Psilocybin isn't a salt and doesn't have a freebase form, it is an indole.  Psilocin is a phosphate ester, and I don't believe it has a salt or freebase form either.  The legitimacy of reports regarding vaporizing either of them are still apparently contested.

SWIM will say that if one were to attempt this, proper heating would be very important.  Apparently, next to nothing will will be extracted by the ethanol without it, though SWIM has only tested it once, and perhaps not thoroughly enough.