A regioselective and highly efficient electrochemical method for direct acylation and carboxylation of a [60]fulleroindoline has been developed. By using inexpensive and readily available acyl chlorides and chloroformates, both keto and ester groups can be easily attached onto the fullerene skeleton to afford 1,2,3,16-functionalized [60]fullerene derivatives regioselectively. In addition, a plausible mechanism for the formation of fullerenyl ketones and esters is proposed, and their further transformations under basic and acidic conditions have been investigated.