First: The D&D alignment system is actually kind of terrible at describing nuanced, three-dimensional characters. I have my own spin on it that makes it more useful.

I think the Good-Evil axis in D&D is best understood as Selfless-Selfish. Evil D&D characters generally aren't soulless and don't go around doing bad things for no reason, they just care more about themselves than others. Good characters may become adventures to make the world a better place; Neutral characters may become adventurers to achieve a goal; Evil characters may become adventurers to get something they want. Good characters are the most likely to go out of their way to help or avoid harming others; Evil characters are least likely to go out of their way for anything.

The Law-Chaos axis may be better understood to indicate a character's relationship to the status quo, including but not limited to government, society, and other external authorities. A Lawful character will actively avoid rocking the boat and will use the current system to achieve their goals; a Chaotic character isn't happy unless they're making waves.

With that in mind:

Jenni is Neutral Good. She wants to help people no matter what it takes, and chafes at the restrictions she's under in the PPC even though she understands why the rules exist and should be followed. Usually.

Supernumerary is Lawful Neutral. Doing what's Right is more important than being Good. He values facts, logic, and the Way Things Are Supposed To Be, possibly because it's hard enough living with his brain without people going and messing things up around him. People are messy, and he doesn't go out of his way to interact with others either to help or to harm, though when the chips are down, he does show up for the few people he values in his life.

Ilraen is Lawful Good, but more Good than Lawful. He believes in the virtue of rules and structure, but only insofar as they actually make the universe a better place. If the rules are hurting people, he'll work to change the rules if possible, but mostly he'll try to help the people. In the present day, he's an agent trainer, because he can't change Upstairs, let alone the Narrative Laws, but he can help new recruits be better prepared to handle things than he was.

Derik is... complicated. He believes he's Lawful Good, but he's actually Chaotic Good—and that's not because of his issues. He comes from a culture in the throes of a sea change, and he was totally on board with the change. Also, he has a history of taking justice into his own hands from a young age and doesn't really respect any particular authority that isn't his own. It's not that he disrespects authority or can't accept leadership from others, but if he thinks the people in charge are being stupid, he will ignore them and do things his own way. His willfulness has gotten him into pretty much every bit of trouble he's ever had in his life, up to and including his recruitment to the PPC.

Gall is Neutral Evil. Her guiding principle is "What's good for me," and she will do precisely whatever it takes to get what she wants regardless of who she has to step on to get there. She respects strength over any sort of moral or civil authority ("might makes right"). However, there ARE lines she won't cross. "Evil" does not mean "must always do the worst thing possible": she's not going to burn down the Nursery (except maybe by accident if a visit with Fellrazer gets out of hand some day); she's not going to murder someone if she can just punch them; she won't betray her friends; she would never force anyone into her bed. It's just... less that it would be wrong, more that it would be more trouble than it's worth to her. Developing feelings for Derik and having a kid is forcing her perspective to shift a bit, though. She could end up True Neutral, maybe even Lawful Neutral.

~Neshomeh

Eledhwen is lawful good. She's a marchwarden back in Rivendell and in a yet-to-be-published backstory stitchup chapter she wanted to help some Sues who had betrayed the League of Mary Sue Factories by getting them into a witness protection-esque thing in New Cal.

Christianne is chaotic good. She's prone to doing dumb things for loved ones, like breaking into a Mary Sue Factory, against the express wishes of the DES, to rescue Eledhwen. She and Eledhwen also sorta peaced out of the PPC around 2015 for a bit, and though Eledhwen could've sworn she filed the paperwork, it might not have registered properly, hence one more mission in 2016. But the impetus to just run off without telling anyone was pure Christianne.

The Disentangler is chaotic neutral. She's mostly friendly, but she's definitely done some bad things in the past, and her joking can occasionally shade into a-hole territory.

The Agent is... true neutral, I suppose? Prone to getting dragged along with the Disentangler, but wanting to be a bit more law-abiding. He and the Disentangler's appearances in Very Kell might best illustrate their differences.

Liu Siyuan is probably lawful neutral, since he abides by the rules and customs of his home continuum to a fault, including allowing it to make him get a bit bullheaded when he culture-clashes with HQ stuff. In the development I've done for him this past year, though, he does show chaotic tendencies, and even evil tendencies -- but since they're highly situation-dependent, I wouldn't say it forms a core part of him.

He doesn't really care that much about society rules. In English stuff, however, he's Lawful Neutral. "The English rules are rules!" That sorta stuff. But society rules? He ran out of shpxes when it comes to following society's rules. Heck, he wears fairly casual clothes always, breaking both PPC's lax dress code of "anything black" and the school's dress code for teachers. He's supposed to wear semi-formal stuff. He curses (except in front of young teens and children), he actively is displeased by some agents' doings, and he doesn't follow courtsey rules that often. But he is neither good nor bad.

As for anyone else, IDK. I haven't really thought about alignments.

-kA

Charlie - A straight-up D&D character, to boot! But yeah, chaotic good. They find joy in others' happiness, but rarely consider law and procedure in their actions, even in the mission field.

Jiwon - True neutral. He’s not actively evil by any means, but he can be fairly lazy and self-centered at times.

Ocotillo - Haven't published anything with her in it yet, unless you count her recruiting and the PPC Hunger Games. Anyway, lawful good, leaning slightly more lawful than good.

Dr. Glocktopus - Honestly, I don't know. Personal alignment didn't really matter for the scenes I wrote it in, so I never really thought about it.

Nikki is the one I'm most sure about - Lawful Good. Corolla is also very definitely Chaotic Good, and Sergio is more of a Neutral Good though he has his Chaotic Neutral moments.

As for my second, pretty much abandoned (in favor of TWWA) spinoff, Keiko pretty much is Neutral Good like her father, while I never fleshed out Shiro and Saki enough to be able to answer this.

To complete the family with TWWA-centric characters, Ami is also very definitely Lawful Good like Nikki, which is also how I see Hajime (though so far she's been a PPC agent in name only as she's from an alternate timeline and I haven't written her in an actual miission)

For all established characters thus far: Winfrey Blaze - Lawful Good. She follows rules, but her good nature oftentimes gets in the way of that obedience. She tries to follow authority, but is distrustful of it at times due to her past. She's a champion for what is good more than what is law, but she is still bound by law.

Seldon Xaal - Neutral Good - Relatively minor character, his good nature and drive to help others doesn't seem tamped by much.

Cid Bain - Chaotic Good - Fought against authority for freedom multiple times. When placed in positions of authority, kept things democratic and loose. Likely to violate protocols to save others.

Sarkan - Neutral or Chaotic Good. Relatively minor character. A certain anarchic bent comes to Sarkan, as well as a profound greed, but he seems a generally stand-up guy.

Wojtek Bearington III - Neutral Good or True Neutral. Always the mystery, it's hard to tell what he's thinking.

Agent Noman - He's certainly obedient to a strict set of mental rules, and he certainly cares about others, but his priorities are so bizarre that it's difficult to pin him exactly. Lawful Good? Neutral?

Epsilion - Lawful Neutral..? A stickler for protocol, cold and withdrawn at times. Oftentimes entertains horrible ideas, usually discards them as impractical, not immoral. Oftentimes talks about the greater good, and not the individual good. Cares deeply for his friends but seems indifferent to others. Possibly Lawful Evil.

Moira is Lawful Good. She is aware of her background as a Sue and therefore overcorrects when it comes to following PPC procedure. She does however respect life and believes that everyone is capable of redemption. After all, she herself was offered a second chance. She doesn't have the life experience quite yet to make judgement calls on when her compassion is warranted. This means she could easily be taken advantage of.

Blank is Chaotic Neutral. She follows the values of the PPC because they align with what she already believes. She doesn't need to rigidly adhere to the rules nor does she need to rebel against them, but she is not true neutral; she values freedom of choice too much. She has no qualms about killing Sues, as she does not consider them people. She's adaptable in the field, but not when her personal status quo is challenged. Sometimes she is arbitrary to annoy and punish people.

I do have a few more characters that I could do this for, but it's already getting late and it's not like they're in any missions yet, so I'd better not. XD

/Ekwy.

Zara is chaotic neutral, Diamond and Doom are lawful neutral, and Thalia… is just chaotic chaos.

Boadicea is probably some sort of combination of neutral and good. She's done some unherioc things, but she has some sort of moral code.