The reaction of fullerene C₆₀ with isocyanoacetates and EtMgBr in the presence of stoichiometric amounts of Ti(Oi-Pr)₄ was studied for the first time. Unlike esters and nitriles of carboxylic acids and isonitriles, isocyanoacetates were found to react with C₆₀ under the developed conditions to give N-unsubstituted pyrrolidinofullerenes. The electrochemical reduction of the C₆₀ derivatives we synthesized was found to proceed less easily than that of C₆₀ but more easily than that of unsubstituted pyrrolidinofullerenes.