Carbon　materials　are　commonly　integrated　with　TiO2　to　achieve　high　carrier　mobility　and　excellent　photocatalytic　performance,　and　the　chemical　bond　between　TiO2　−　C　is　considered　as　a　significant　strategy　to　enhance　efficiency.　Nevertheless,　few　analyses　have　elucidated　the　formation　mechanism　of　Ti3　+　−　C　bonds　and　the　underlying　reasons　for　the　performance　enhancement.　To　address　these　issues,　this　study　conducts　an　in-depth　investigation　into　the　electronic　structure　of　TiO2　−　C　and　demonstrates　that　the　charge　in　the　nonbonding　molecular　orbital　t2g　of　Ti3　+　is　transferred　to　the　unoccupied　2p　energy　level　of　C　through　the　formation　of　1π　and　2π　bonds,　i.e.,　(Ti　3dxz　-　C　2py)　and　(Ti　3dxy　-　C　2px).　The　hybridization　of　t2g-2p　orbitals　endows　the　Ti3　+　−　C　bond　with　higher　carrier　mobility　and　a　stronger　binding　force,　thereby　contributing　to　stable　photocatalytic　H2　production.　Inspired　by　this　scenario,　the　NSTiO2/rGO　hybrid　architecture,　featuring　the　{101}/{001}　surface　heterojunction　and　the　Ti3　+　−　C　interfacial　chemical　bond,　has　been　constructed.　As　a　result,　the　hybrid　catalyst　exhibited　excellent　photocatalytic　cycling　stability　of　(Formula　presented.)　and　an　H2　evolution　rate　of　33.4　mmolh−1g−1.　This　work　proposes　a　strategy　for　designing　efficient　photocatalyst　by　regulating　orbitals　to　achieve　high-performance　photocatalytic　methanol splitting.　©　2024　Wiley-VCH　GmbH.