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　unparalleled　non-classical　(NC)　isomer　C1-C68(NC3)　and　the　chlorinated　derivative　C1-C68(NC3)Cl28　with　its　partially　hydrolyzed　derivatives　C1-C68(NC3)Cl26(OH)2　and　C1-C68(NC3)Cl25(OH)3,　along　with　the　classical　non-IPR　(isolated　pentagon　rule)　fullerene　C2v-#6073C68　and　its　metal　carbide　clusterfullerene　Sc2C2@C2-#6073C68　have　been　calculated　at　the　density-functional-theory　(DFT)　level.　The　electronic　structures　and　X-ray　spectra　of　classical　and　non-classical　fullerenes　are　undoubtedly　distinguished　from　their　counterparts,　as　are　the　substances　that　have　undergone　chlorination.　The　two　derivatives　produced　in　the　partial　hydrolysis　of　chloride　C1-C68(NC3)Cl28　also　exhibit　distinctive　properties.　The　＇fingerprint＇　in　X-ray　spectroscopy　is　capable　of　offering　an　effective　tool　for　the　identification　of　the　aforementioned　isomers,　as　evidenced　by　the　reality　that　the　XPS　and　NEXAFS　spectra　demonstrate　isomer　dependence.　Ultraviolet-visible　(UV-vis)　absorption　spectroscopy　of　Sc2C2@C2-#6073C68　was　carried　out　using　time-dependent　(TD)　DFT　calculations.　The　emulated　results　and　the　outcomes　of　the　experiment　coincide　well.　This　study　indicates　how　X-ray　and　UV-vis　spectroscopy　methods　can　provide　valuable　data　to　support　researchers　in　exploring　the　electronic　structure　of　fullerene　materials　and　the　identification　of　isomers　in　both　further　experimental　and　theoretical　disciplines.　©　2024　The　Royal　Society　of　Chemistry.