Different fullerene-grafted poly(N-vinylcarbazole) was synthesized by free radical polymerization and the influence of the amount of initiator, the reaction time and the reaction temperature on the polymerization was studied. Metallofullerene-grafted polymer (Gd@C82-PVK) was firstly synthesized and characterized by GPC, UV-vis, FTIR, DSC, XPS. The results demonstrated that the fullerenes had chemically combined with PVK. Fluorescence spectra suggested that the grafted fullerenes had certain influence on the fluorescence properties of the polymer. This is due to the better electron-attractive ability of fullerenes, which contributed a lot to form the electron donor-acceptor systems in fullerene-grafted poly(N-vinylcarbazole). Potential applications of this kind of materials in optical and memory devices were expected.