Six C-34 isomers were theoretically identified by X-ray photoelectron spectra (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra. The XPS and NEXAFS spectra of K-edge for all non-equivalent carbon atoms were simulated by density functional theory method combined with the full core-hole potentials. The XPS spectra mainly showed dependence on the isomers with different symmetries. Strong isomer identification of the NEXAFS spectra for C34 was found and discussed in detail. Furthermore, the spectra components of carbon atoms with different local environment were explored. The NEXAFS spectra dependence on the local structure of fullerene was discussed as well. (C) 2015 Elsevier B.V. All rights reserved.