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Abstract Surface hybrid inorganic semiconductors photocatalysts with π conjugated structure have recently been widely used in the field of photocatalytic environmental remediation and energy conversion. Surface hybridization is considered to be an efficient way to significantly enhance the photocatalytic activity by several times, completely inhibit photocorrosion of inorganic photocatalysts and expand the spectral response range of photocatalysts. This review provides a comprehensive overview of the surface hybridization definition, the principle of enhancing photocatalytic performance and the control factors of surface hybridization to promote photoactivity. Summarize the preparation and structural identification method of the surface hybrid photocatalyst. Special emphasis is placed on the various photocatalytic system construction of surface hybridization. The development of surface hybrid photocatalysts for pollutant degradation and energy conversion are further presented. Finally, the challenges and future development prospects of surface hybridization in photocatalysis are discussed. We hope this critical review can provide a clear picture of the state‐of‐the‐art achievements and facilitate the applications of surface hybrid photocatalysts in environmental remediation and energy conversion.