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So i'm still fairly new to the psychic phase with my army of Daemons and I was curious if greater daemons are able to take advantage of both focus'.

An example being a Great Unclean One at mastery level 3. Chaos focus says it will simply get the Plague Disciplines primaris for free no matter what discipline I choose to generate from. If i were to generate all 3 powers from lets say Biomancy, would I get smite for free as well from regular focus? The definition of regular focus stated if I actually generated all my powers from the same, then i'd get the primaris for free leading me to believe in this case i'd get smite as well. Just wanted to confirm and make sure i'm not going taking extra powers. Thank you.

The FAQ says no you can't get both focus

Which FAQ? The Warhammer 40K Rulebook FAQ on GW updated in November doesn't mention that at all and the Daemon FAQ updated in 2014 does not say that either?

 CrownAxe wrote:
The FAQ says no you can't get both focus

This is not the case at all. The updated BRB FaQ doesn't state in favour of either opinion (yes they get both/no they don't get both) and neither does the current Daemons FaQ.

However the Draft FaQ for Daemons says they get both:

Q: If a Chaos Daemon Psyker generates all of their powers from a single discipline from Warhammer 40,000: The Rules, does he benefit from Psychic Focus in addition to Chaos Psychic Focus (as the mandatory primaris power from Chaos Psychic Focus isn’t generated as such)?
A: Yes

Link

Alright sweet, thank you!