Boron-doped C 6 0 films were synthesized by the radio frequency plasma assisted vapor deposition. Characterizations of the samples was performed by Fourier transform infrared spectroscopy, Raman spectroscopy, UV-visible absorption measurements and photoluminescence spectroscopy. The results show that the higher energies and densities of the reactive radicals in the plasma are favorable to form B-doped C 6 0 molecules. The UV-visible absorption spectra and photoluminescence spectra of the B-doped C 6 0 films exhibit some difference from that of a pristine C 6 0 film, which is due to the lower symmetry of the B-doped C 6 0 film. In addition, the polymerization of C 6 0 molecules was also observed during the deposition besides the formation of the boron-doped C 6 0 molecules.