As a promising two‐dimensional conjugated polymer, graphitic carbon nitride (g‐C3N4) has been utilized as a low‐cost, robust, metal‐free, and visible‐light‐active photocatalyst in the field of solar energy conversion. This Review mainly describes the latest advances in g‐C3N4 photocatalysts for water splitting. Their application in CO2 conversion, organosynthesis, and environmental purification is also briefly discussed. The methods to modify the electronic structure, nanostructure, crystal structure, and heterostructure of g‐C3N4, together with correlations between its structure and performance are illustrated. Perspectives on the challenges and opportunities for the future exploration of g‐C3N4 photocatalysts are provided. This Review will promote the utilization of g‐C3N4 materials in the fields of photocatalysis, energy conversion, environmental remediation, and sensors. Metal‐free photocatalysis: Recent progress in g‐C3N4 photocatalysis is highlighted. The four fundamental approaches for modification of g‐C3N4 photocatalysts are discussed: electronic structure modulation, nanostructure design, crystal‐structure engineering, and heterostructure construction. The application of g‐C3N4 photocatalysts are briefly summarized and the opportunities and challenges in this field are discussed.