Efficient utilization of near-infrared (NIR) energy is a high-priority in the field of energy and nanomedicine, yet the design and assembly of metal-free NIR-driven photocatalysts with biologic safety and good stability is still challenging. Herein, we report the design and synthesis of high-quality metal-free NIR-driven photocatalysts by judiciously combining the US Food and Drug Administration (FDA)-approved clinically useable Chlorin e6 (Ce6) as NIR photosensitizer and the protonated two-dimensional (2D) graphitic carbon nitride (g-C₃N₄) for the first time. Under the irradiation of visible light (>420 nm) and NIR light (>780 nm), the Ce6@pCN prepared here showed remarkable 10-fold and 174-fold high H₂ evolution performance compared with bulk g-C₃N₄ (1275.6 vs. 127.1 μmol h⁻¹ g⁻¹; 312.6 vs. 1.8 μmol h⁻¹ g⁻¹) and excellent stability. Owing to the high efficiency, stability and nontoxicity, this protonated 2D g-C₃N₄ sensitized with Ce6 is promising for a wide-range of applications in energy, environmental and biological fields.