Fullerenation of polycarbonate (PC), a commercially important optical polymer, was achieved by direct reaction of C-60 and PC in the presence of azo-bis-isobutyronitrile (AIBN), using 1,1,2,2-tetrachloroethane as the solvent under microwave irradiation (MI). Compared with conventional heating process, MI could significantly enhance the rate of the fullerenation under identical reaction conditions. The C-60 content of the fullerene-functionalized polycarbonate (C-60-PC) could be controlled via varying the C-60/PC feed ratio and the reaction time. The C-60-PCs are soluble in common organic solvents such as THF and chloroform. The products were characterized by gel permeation chromatography, UV-vis, FTIR, TGA, DSC, H-1 NMR, and C-13 NMR. The reaction of C-60 with PC under MI was monitored by electron spin resonance spectra, the fullerene radicals were detected in reaction solutions and also in the solid product polymers, indicating the radical mechanism of the reaction. The nonlinear optical property of C-60-PCs in THF was investigated by the open-aperture z-scan technique at 527 nm, and its nonlinear absorption coefficient was found to be in the same order as that of C-60.