Nitrogen-deficient graphitic carbon nitride (g-C3N4−x) was synthesized by a hydrothermal treatment using ammonium thiosulfate as an oxidant. The as-prepared photocatalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption–desorption, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), elemental analysis (EA), electron paramagnetic resonance (EPR), UV-vis diffuse reflectance spectroscopy (UV-vis DRS) and photoluminescence (PL) spectroscopy. The visible-light-driven photocurrent measurement was performed by several on–off cycles of intermittent irradiation. The photocatalytic activity of catalysts was evaluated by splitting water under visible-light irradiation (λ > 420 nm). Results demonstrated that the photoactivity of g-C3N4−x was enhanced greatly by the deficiency of the terminal amino species on the catalysts. The average H2 evolution rate on g-C3N4−x was 31.6 μmol h−1, which was ca. 3 times higher than that on pristine g-C3N4. It was revealed that the unique nitrogen-deficient structure of g-C3N4−x played an important role in broadened visible-light absorption and efficient electron–hole separation, mainly accounting for the improved photocatalytic activity.