One kills when SAS stray from path (8)
I believe the answer is:
assassin
'one kills' is the definition.
'when sas stray from path' is the wordplay.
'when' becomes 'as' (eg 'when I walked' means 'as I walked').
'stray from path' becomes 'sin'.
'as'+'sas'+'sin'='ASSASSIN'
(Other definitions for assassin that I've seen before include "Professional, often political, killer" , "Booth, for example" , "One making hits" , "Hired murderer" , "Hitman" .)