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However, its efficiency is often hindered by rapid electron\u2013hole recombination. Covalent organic frameworks (COFs)\u2014a class of crystalline, porous organic polymers\u2014offer exceptional potential for photocatalysis owing to their precisely tunable structures and distinctive physicochemical properties, yet their performance remains limited by intrinsic charge recombination. To overcome this limitation, the construction of S\u2010scheme heterojunctions has been proposed as a promising strategy to enhance charge separation while maintaining strong redox capabilities. This review begins by presenting a comprehensive perspective on the development and scientific significance of S\u2010scheme heterojunctions. It then systematically summarizes the design principles and synthetic strategies of COFs, followed by an in\u2010depth discussion of the fabrication methods and principles of COF\u2010based S\u2010scheme heterojunctions. Furthermore, advanced characterization techniques that enable precise elucidation of charge migration pathways within these heterostructures are highlighted. The review also provides a comprehensive overview of recent applications of COF\u2010based S\u2010scheme photocatalysts, including hydrogen evolution, carbon dioxide reduction, environmental remediation, hydrogen peroxide production, and others. 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