X-ray　photoelectron　(XPS)　and　near-edge　X-ray　absorption　fine　structure　(NEXAFS)　spectra,　as　well　as　the　ground-state　electronic/geometrical　structures　of　two　important　isomers　of　the　elusive　C72　fullerene　family　(C2v-　and　D6d-symmetry,　respectively)　and　the　corresponding　chlorinated　derivative　C72Cl4,　which　are　newly　captured　in　the　experiment,　have　been　simulated　at　the　density　functional　theory　(DFT)　level.　Effective　changes　in　the　electronic　structure　and　simulated　X-ray　spectra　have　been　observed　after　chlorination.　Both　spectra　show　strong　isomer　dependence,　therefore　the　＂fingerprints＂　in　the　X-ray　spectra　offer　a　useful　method　for　isomer　identification　of　the　above-mentioned　fullerenes.　The　ultraviolet-visible　(UV-vis)　absorption　spectroscopy　of　C72Cl4　has　also　been　performed　by　means　of　time-dependent　(TD)　DFT　calculations.　The　simulated　UV-vis　spectrum　is　in　good　agreement　with　the　experimental　results.　The　results　of　this　work　can　provide　valuable　information　for　further　experimental　and　theoretical　studies　on　newly　synthesized　fullerene　isomers　and　their　derivatives　by　means　of　X-ray　and　UV-vis　spectroscopy　techniques.　©　the　Owner　Societies　2016.