A novel type of fullerene derivatives, [60]fullerothiazolidinethiones (2), were obtained from the copper-catalyzed aerobic oxidative reaction of C60 with aliphatic primary amines and CS2 in 4:1 v/v DMF and o-DCB. The obtained products were fully characterized with the X-ray single-crystal diffraction and spectroscopic methods. Control experiment with maleic anhydride, an analogue to C60, also afforded thiazolidinethione product, but via a mechanism different from that of C60 judging from the structure difference between the two types of thiazolidinethione compounds, demonstrating the unique reactivity of C60.