Old footballer chucking last boot out (5)
I believe the answer is:
expel
'boot out' is the definition.
(synonyms)
'old footballer chucking last' is the wordplay.
'old' becomes 'ex' (prefix meaning former or onetime).
'footballer' becomes 'pele' (Brazilian footballer Pele).
'chucking last' means to remove the last letter (the last letter is chucked away).
'pele' with its final letter removed is 'pel'.
'ex'+'pel'='EXPEL'
(Other definitions for expel that I've seen before include "Put out" , "Force to leave" , "Ban from school" , "Drive out - dispossess" , "Get rid" .)