As the title says; How well does it work?
Do you mean as a player character?
Yes.
I'm generally not a fan of one player's character betraying the others and working to subvert what they're doing.... I run my games co-op, not PvP.
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Well, one of the pre-generated characters made specifically for this adventure is an antipaladin of Mazmezz, so there must be some room for the concept. Keep in mind that there is no Blood War in the Pathfinder setting, so there is no conflict between Demons and Devils beyond conflicting personalities.
However, the above mentioned antipaladin seems to be open about his allegiance and is just there to smash stuff and make a mess. I don't really know how someone who tries to hide his allegiance to demons would work out.
Well, one of the pre-generated characters made specifically for this adventure is an antipaladin of Mazmezz, so there must be some room for the concept. Keep in mind that there is no Blood War in the Pathfinder setting, so there is no conflict between Demons and Devils beyond conflicting personalities.
However, the above mentioned antipaladin seems to be open about his allegiance and is just there to smash stuff and make a mess. I don't really know how someone who tries to hide his allegiance to demons would work out.
That's Hell's Vengeance, not Hell's Rebels.
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Assuming you don't mind having CE characters in your campaign, a demon worshipper could have as much reason to oppose Thrune as a paladin. But I'm inclined to agree with Cole that you'd want your players to be working together. For my part, I did not allow any evil PCs in my game. There are better APs for evil characters, Hell's Vengeance and Skull & Shackles being the ones that immediately come to mind.
Considering the number of players I am likely to have might it work as a subplot with a GMNPC?
I think I want to hear why this idea has occurred to you before weighing in... what's the goal, a supposedly trusted ally twirling his mustache and summoning a Balor in the third act, a shady guy proving he can't be trusted, or what?
Between running the rebellion, cracking heads, and orchestrating the social angles of the adventures as written there's already a lot going on.
Something of a redemption angle. The character would go from apathetic agent to "I'm damned, but i'll make good use of my time before my soul comes due." I can see the character offering a different perspective in his/her situation and being a reminder of compassion... Unless they kill the character in which case it will reaffirm any extreme tendencies they might have.
Then again it could be an infernal mole but that seems less likely than a demonic one.