The reactions of C-60 and trichloromethyl anion (CCl3-) via both the Bingel mechanism and the carbene mechanism were comparably studied by means of density functional theory (DFT) computations. The Binge] mechanism is highly competitive as compared with the carbene mechanism that leads to the formation of C-60(CCl2). Unlike the carbene mechanism with a weak regioselectivity and solvent sensitivity, the Bingel mechanism yields the [6,6]-C-60(CCl2) isomer as the exclusive product and favors highly polar solvents. The results receive strong experimental support and simultaneously rationalize these experimental findings.