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I've been getting a bit of a writing itch and am wanting to try writing a story following a Psyker in the Imperium of Man. I haven't decided if I want them to be attached to a Guard Regiment or serving an Inquisitor yet, as both provide interesting elements. And while my copy of Ciaphas Cain: Hero of the Imperium and IG codex provide useful information, I'd still like a little more to go off of. I saw on another thread that the Eisenhorn books provide a good look at the Inquisition, but are there any other books that prominently feature Psykers and/or Inquisitors (ideally as main characters)?

There's one in outcast dead.

Not sure if its exactly what your after though as not quite main, but there role in book is a big one. Goes into a bit of detail on telapthica, the city of the blind etc and also goes slightly into the navigators.

Shows how underclass of Terra live though,

Ravenor is a main character psyker? Same with any Grey Knight based book.

Talon of Horus, main character is a Psyker.

THere's a secondary plot about a psyker in the Gaunt books - five through seven, I think?