Direct fullerenation of polycarbonate (PC), a commercially important optical polymer, is achieved by simply irradiating a solution of PC and C-60 at room temperature using a conventional UV lamp or by warming up a C-60/PC solution to a moderate temperature (60 degrees C) in the presence of AIBN, a typical radical initiator. The extent of fullerenation is controllable by varying the C-60 feed ratio, and a fullerenated PC with a C-60 content as high as 6.3 wt % (or more than two C-60 molecules per PC chain) is readily prepared in almost quantitative yield (99.7%). Molecular weights of the fullerenated PCs are higher than that of the parent polymer, suggesting that the fullerenation is realized via multiaddition to C-60. The multiaddition, however, has not led to heavy cross-linking, and the fullerenated PCs are soluble in common organic solvents such as THF and chloroform. The fullerenation involves a radical mechanism, and its general applicability to other polymer systems is demonstrated by the ready attachment of C-60 to poly(vinyl chloride), another commercially important polymer, by employing the AIBN-initiated fullerenation reaction.