Illegal substance CIA once concocted (7)
I believe the answer is:
cocaine
'illegal substance' is the definition.
'cia once concocted' is the wordplay.
'concocted' is an anagram indicator.
'cia'+'once'='ciaonce'
'ciaonce' anagrammed gives 'COCAINE'.
(Other definitions for cocaine that I've seen before include "Recreational drug" , "Number" , "Drug, crack" , "Charlie" , "Strange oceanic narcotic" .)