It depends on what type of machine/encoding generated your import file.
If you're getting it from an English or Western European version of Windows, your best bet is probably setting it to 'WIN1252'. If you are getting it from a different source, consult the list of character encodings here:
http://www.postgresql.org/docs/8.3/static/multibyte.html
If you're getting it from a Mac, you may have to run it through the "iconv" utility first to convert it from MacRoman to UTF-8.