AbstractCarbon 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 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.