Photocatalysis is considered to be an effective way to remove organic pollutants, but the key to photocatalysis is finding a high-efficiency and stable photocatalyst. 2D materials-based heterojunction has aroused widespread concerns in photocatalysis because of its merits in more active sites, adjustable band gaps and shorter charge transfer distance. Among various 2D heterojunction systems, 2D/2D heterojunction with a face-to-face contact interface is regarded as a highly promising photocatalyst. Due to the strong coupling interface in 2D/2D heterojunction, the separation and migration of photoexcited electron-hole pairs are facilitated, which enhances the photocatalytic performance. Thus, the design of 2D/2D heterojunction can become a potential model for expanding the application of photocatalysis in the removal of organic pollutants. Herein, in this review, we first summarize the fundamental principles, classification, and strategies for elevating photocatalytic performance. Then, the synthesis and application of the 2D/2D heterojunction system for the removal of organic pollutants are discussed. Finally, the challenges and perspectives in 2D/2D heterojunction photocatalysts and their application for removing organic pollutants are presented. Display omitted •The fundamental principles and synthesis methods of 2D/2D heterojunction.•Type I, type II, p-n junction, Z-scheme, S-scheme and Schottky junction.•The photodegradation performance of 2D/2D heterojunction systems.•The current challenges and future development directions of 2D/2D heterojunctions.