From Kiev a defector to escape (5)
I believe the answer is:
evade
'to escape' is the definition.
(evading is a kind of escaping)
'from kiev a defector' is the wordplay.
'from' indicates the answer is hidden within the clue.
'EVADE' can be found hidden inside 'kiev a defector'.
(Other definitions for evade that I've seen before include "Dodge by cleverness (5)" , "temptress conveying commercial message" , "Dodge or equivocate" , "Dodge - prevaricate" , "Sidestep" .)