"Comedy hero always looked knowingly youthful," starts White (6)
I believe the answer is:
chalky
'white' is the definition.
('chalky' can be similar in meaning to 'white')
'comedy hero always looked knowingly youthful starts' is the wordplay.
'starts' suggests taking the first letters.
The first letters of 'comedy hero always looked knowingly youthful' is 'CHALKY'.
(Other definitions for chalky that I've seen before include "Mr White" , "White coloured" , "Dusty" .)