Starts upsetting the peons (5)
I believe the answer is:
opens
'starts' is the definition.
(opening is a kind of starting)
'upsetting the peons' is the wordplay.
'upsetting' indicates an anagram.
'peons' is an anagram of 'OPENS'.
(Other definitions for opens that I've seen before include "Unseals" , "competitions welcoming all-comers" , "releases" , "Unlocks" , "Exposes, begins" .)