in the Facebook sense, attested from November 2007, from un- (1) "not" + friend (v.). Unfriended is at least as old as Shakespeare in the sense "friendless." A noun unfriend "enemy" is recorded from late 13c., chiefly in Scottish, and was still in use in the 19th century.
unfortunately
unfortune
unfounded
unfree
unfrequented
unfriend
unfriendly
unfruitful
unfulfilled
unfunded
unfunny