c. 1300, "unaccustomed," from un- (1) "not" + past participle of use (v.). Meaning "not employed" is recorded from late 14c.
an unused envelope
we bought an unused car for a change
untrustworthy
untruth
unturned
untwist
unusable
unused
unusual
unutterable
unvanquished
unvarnished
unvarying