The photocatalytic production of solar hydrogen through water splitting by graphitic carbon nitride (g-C3N4) has gained substantial interest due to its advantageous characteristics, such as eco-friendliness, wealth on the earth, favorable bandgap, and easy preparation. Nevertheless, the performance for photocatalytic overall water splitting has been significantly restricted owing to the rapid recombination of charge carriers and slow catalytic kinetics. This investigation demonstrates the utilization of a single-atom Ni-terminating agent to coordinate with the heptazine moieties of g-C3N4, resulting in the formation of a new electronic orbital. g-C3N4 with single-atom Ni-termination can achieve highly efficient photocatalytic overall water splitting into H2 and H2O2 upon visible light irradiation, without requiring the use of any additional cocatalysts. The underlying cause of the enhanced photocatalytic performance of single-atom Ni-incorporated g-C3N4 in hydrogen evolution reaction is identified using synchrotron X-ray spectroscopy and microscopy. The X-ray spectro-microscopic results discover that the new hybrid orbital that is critical for optimizing photocatalysis is associated with carbon defects. The atomic and electronic structures and the band gap of g-C3N4 are adjusted by the new hybrid orbital. Moreover, it synergistically enhances visible light absorption, thereby promoting the separation and transfer of photogenerated charge carriers. The single-atom Ni and the adjacent C atom are recognized as the active sites for water oxidation and reduction, respectively, supporting the efficient photocatalytic splitting of water via a two-electron transfer pathway. This study demonstrated a promising material design for promoting photocatalytic activity in solar energy conversion applications.