Shoe not originally for villain (5)
I believe the answer is:
rogue
'for villain' is the definition.
(rogue is a kind of villain)
'shoe not originally' is the wordplay.
'shoe' becomes 'brogue' (brogue is a type of shoe).
'not originally' means to remove the first letter (the origin of the word is removed).
'brogue' with its first letter taken away is 'ROGUE'.
(Other definitions for rogue that I've seen before include "A dishonest or unprincipled person" , "Scoundrel, knave" , "Scally" , "Villain - freak" , "Blackguard" .)