<p>In recent years, covalent organic frameworks (COFs) have been rapidly developed due to their advantages, including high specific surface area, stable pores, and stable chemical structures. This has led many researchers to recognize the significant potential of COFs in catalysis, adsorption, and energy storage. The functionality of COFs can be precisely designed through approaches such as modifying building monomers and post-synthetic modification, thus expanding the possibilities for materials development. Topological structures significantly impact the photocatalytic performance, influencing light absorption, photoelectron transfer, and charge carrier migration. Previous studies have underscored the significance of topological structures in COFs-based photocatalysis; however, a comprehensive review remains lacking. To this end, this review focuses on revealing the structure-activity relationship between topological structures and COFs-based photocatalysis, based on an analysis of the photocatalytic mechanism and enhancement mechanisms of topological COFs. In particular, this review systematically elaborates on advances in enhancing photocatalysis of one-dimensional (1D), 2D, and 3D topological COFs. Moreover, the design and modification strategies of topological COFs, including pre-synthesis and post-synthesis regulation strategies, have also been carefully summarized to further enhance their photocatalytic performance. It is anticipated that this review can provide important references and guidance to achieve the efficient development of topological structures in the field of COF photocatalysis.</p>