In this study, methanofullerenes and 2',3'-dihydrofuran C 60 derivatives were selectively synthesized in high yields via the reactions of C 60 with β-keto esters under mild conditions by controlling the addition sequence and molar ratio of iodine and base. The structures of the products were determined by spectroscopic characterization. Moreover, a possible reaction mechanism for the selective formation of fullerene derivatives was proposed.