X-ray　photoelectron　spectroscopy　(XPS)　and　near-edge　X-ray　absorption　fine　structure　(NEXAFS)　spectra,　as　well　as　the　ground-state　electronic/geometrical　structures　of　the　newly　discovered　two　non-classical　isomers　C2-C76(NC2)　and　C1-C76(NC3)　with　their　derivatives　C2-C76(NC2)(CF3)14　and　C1-C76(NC3)Cl24,　as　well　as　the　non-IPR(isolated　pentagon　rule)　isomer　C1-#17418C76　with　its　embedded　metal　fullerene　U@C1-#17418C76　have　been　calculated　at　the　density　functional　theory　(DFT)　level.　The　electronic　structure　after　chlorination　is　significantly　different　in　the　simulated　X-ray　spectrum.　Both　XPS　and　NEXAFS　spectra　reflect　obvious　isomer　dependence,　indicating　that　the　＇fingerprint＇　in　X-ray　spectroscopy　can　provide　an　effective　means　for　the　identification　of　the　above-mentioned　fullerene　isomers.　Time-dependent　DFT　was　used　to　simulate　the　ultraviolet-visible　absorption　spectrum　of　U@C1-#17418C76.　The　calculated　results　are　in　good　agreement　with　the　experimental　consequence.　This　work　reveals　that　theoretically　simulated　X-ray　and　UV-vis　spectroscopy　techniques　can　provide　valuable　information　to　help　researchers　explore　the　electronic　structure　of　fullerenes　and　the　identification　of　isomers　in　future　experimental　and　theoretical　fields.　©　2022　American　Chemical　Society