C-60 chemically modified poly(N-vinyl-chloromethylcarbazole) was synthesized by the reaction of C-60 with living poly( N-vinyl-chloromethylcarbazole) (PVCC) carbanions, which were prepared by alpha-position proton abstraction with NaH. The structural characterization techniques used were ultraviolet-visible, Fourier transform-infrared spectroscopy, X-ray diffraction, scanning electron microscopy, nuclear magnetic resonance and electron spin resonance, etc. All experimental results proved that C-60 was covalently attached on the backbone chain of PVCC and consequently causes a remarkable enhancement of the photoconductivity of the parent polymer. Also, it was found that fullerenation of PVCC modified both the electronic structures of the carbazole pendant group and the interchain structure.