Semiconductor‐based photocatalysis technology has attracted widespread attention due to its great potential for solving both energy and environmental problems through direct utilization of inexhaustible solar energy. Among various photocatalysts, 2D/2D Z‐scheme heterojunctions exhibit superior performance in various photocatalytic applications, due to their large interfacial contact and rapid Z‐scheme charge transfer with the efficient separation of photogenerated charge carriers and maximized redox ability. In this review, the historical development of, requirements for the formation of, and identification methods of Z‐scheme heterojunctions are first introduced, followed by the summary of important advantages of 2D materials and 2D/2D heterojunctions in photocatalysis. Subsequently, a special focus is put on the recent advances of 2D/2D Z‐scheme heterojunctions for photocatalytic applications, including photocatalytic H2 production, CO2 reduction, and degradation of pollutants. Finally, a brief summary and perspectives on the challenges and future research topics of 2D/2D Z‐scheme heterojunction photocatalysts are presented.