C is X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra for three C-66 fullerene isomers and related chlorinated species have been calculated by density functional theory (DFT) method. The XPS spectra show isomer dependence for the three, pristine C-66 isomers but not for the chlorinated species. The NEXAFS spectra exhibit strong dependence on the structures of all the investigated molecules and thus can be well employed to identify the three C-66 fullerene isomers and related chlorinated species. Both XPS and NEXAFS spectra of the chlorinated species present significant variations compared with the pristine fullerenes. The spectral components for carbon atoms of different local environments have been explored as well. The spectra for the carbon atoms connecting to chlorine atoms exhibit a significant blue shift compared to the others.