Unoccupied head of company in road, self-employed (9)
I believe the answer is:
freelance
'self-employed' is the definition.
(synonyms)
'unoccupied head of company in road' is the wordplay.
'unoccupied' becomes 'free' (similar in meaning).
'head of' says to take the initial letters.
'in' indicates putting letters inside.
'road' becomes 'lane' (a lane is a small road).
The initial letter of 'company' is 'c'.
'c' inserted inside 'lane' is 'lance'.
'free'+'lance'='FREELANCE'
(Other definitions for freelance that I've seen before include "Not tied to employer" , "Writer or artist who sells services to different employers" , "He works alone" , "Self-employed person offering services where needed" , "Of journalist, one who works for several employers, self-employed" .)