It depends what follows the preposition. If you are talking about travelling (i.e. "been" is past participle of "to go"), then "to" is correct:
e.g. I have never been (travelled) to Ukraine.
If you are talking about position (i.e. been is past participle of "to be"), then "in" might be a good choice of preposition
e.g. I have never been in trouble / in hospital.
There may be some ambiguous situations like prison. It's usual to say : "I have never been to prison", which means "I have never been imprisoned".
But if you wanted to clarify that you had never been inside a prison building, you should use "in" or "inside".