S-scheme heterojunctions have become a hot topic in photocatalysis. Copper (Cu) compounds are a versatile family of photocatalytic materials, including oxides (CuO, Cu₂O), binary oxides (CuBi₂O₄, CuFe₂O₄), sulfides (Cu_xS, (1 ≤ x ≤ 2)), selenides (CuSe), phosphides (Cu₃P), metal organic frameworks (MOFs), etc. These materials are characterized by narrow bandgaps, large absorption coefficients, and suitable band positions. To further increase the efficiency of photoinduced charge separation, Cu-based photocatalytic materials are widely integrated into S-scheme heterojunctions and exploited for the hydrogen evolution reaction (HER), CO₂ reduction, H₂O₂ generation, N₂ fixation, and pollutant degradation. This review comprehensively discusses recent progress in Cu-based S-scheme heterojunctions, and highlights their considerable potential for targeted applications in sustainable energy conversion, environmental remediation, and beyond. The fundamentals of S-scheme charge transfer, the design principles and verification tools are summarized. Then, the review describes the Cu-based photocatalytic materials, categorized according to their chemical composition, and their integration in S-scheme heterojunctions for photocatalytic applications. In particular, the implications of the S-scheme charge transfer mechanism on promoting the catalytic activity of selected systems are analyzed. Finally, current limitations and outlooks are provided to motivate future studies on developing novel and advanced Cu-based S-scheme photocatalysts with high performance and studying the underlying photocatalytic mechanisms.