I want to know country of some person.
What's right question?
What country is he from? OR From what country is he?
Or maybe the both options are wrong, aren't?
English Language Learners Stack Exchange is a question and answer site for speakers of other languages learning English. It only takes a minute to sign up.Sign up to join this community
What country is he from?
This is the way I would say it. Perhaps you're worried about using that version, because you were told it was not proper to end a sentence with a prepostion. That piece of advice is widely disregarded nowadays. Simple type this into Google:
Is it okay to end a sentence with a prepostion
and you'll find plenty of credible sources assuring you that doing so is not a problem.
Your second version is not ungrammatical, but it does sound stilted.