The　geometrical　electronic　structures　of　eight　N,　P　co-doped　graphene　molecules　and　their　possible　oxidized　derivatives　have　been　explored　as　well　as　their　C　1　s　and　N　1　s　X-ray　photoelectron　spectra　(XPS)　and　near-edge　X-ray　absorption　fine　structure　spectra　(NEXAFS)　have　been　simulated　at　the　density　functional　theory　(DFT)　level.　The　simulated　spectra　agree　good　with　the　experimental　results.　The　combination　of　the　XPS　spectra　and　NEXAFS　spectra　can　give　effective　information　for　the　structural　identification　of　the　eight　N,　P　double-doped　graphene　molecules.　©　2025　Elsevier　B.V.