At least in the general case, there's no way to be certain what encoding is used for a file -- the best you can do is a reasonable guess based on heuristics. You can eliminate some possibilities, but at best you're narrowing down the possibilities without confirming any one. For example, most of the ISO 8859 variants allow any byte value (or pattern of byte values), so almost any content could be encoded with almost any ISO 8859 variant (and I'm only using "almost" out of caution, not any certainty that you could eliminate any of the possibilities).
You can, however, make some reasonable guesses. For example, a file that start out with the three characters of a UTF-8 encoded BOM (EF BB BF), it's probably safe to assume it's really UTF-8. Likewise, if you see sequences like: 110xxxxx 10xxxxxx, it's a pretty fair guess that what you're seeing is encoded with UTF-8. You can eliminate the possibility that something is (correctly) UTF-8 enocded if you ever see a sequence like 110xxxxx 110xxxxx. (110xxxxx is a lead byte of a sequence, which must be followed by a non-lead byte, not another lead byte in properly encoded UTF-8).