摘要: Solar-driven photocatalytic overall water splitting (POWS) has emerged as a sustainable pathway for hydrogen production, yet faces intrinsic challenges in developing robust catalysts that balance efficiency, stability, and cost-effectiveness. Polymeric carbon nitride (PCN) represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability. Nevertheless, limited by rapid charge recombination and insufficient oxidative capability, little success has been achieved on pristine PCN photocatalyst in POWS. In this context, recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance. Based on the fundamental principles of photocatalysis, this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems. With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems, modification strategies including crystallinity engineering, supramolecular precursor design, cocatalyst modulation, and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years. Future perspectives for PCN-based photocatalysts are proposed, aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.