AbstractPhotocatalysis is a green technology to use ubiquitous and intermittent sunlight. The emerging S‐scheme heterojunction has demonstrated its superiority in photocatalysis. This article covers the state‐of‐the‐art progress and provides new insights into its general designing criteria. It starts with the challenges confronted by single photocatalyst from the perspective of energy dissipation by borrowing the common behaviors in the dye molecule. Subsequently, other problems faced by single photocatalyst are summarized. Then a viable solution for these problems is the construction of heterojunctions. To overcome the problems and mistakes of type‐II and Z‐scheme heterojunctions, S‐scheme heterojunction is proposed and the underlying reaction mechanism is summarized. Afterward, the design principles for S‐scheme heterojunction are proposed and four types of S‐scheme heterojunctions are suggested. Following this, direct characterization techniques for testifying the charge transfer in S‐scheme heterojunction are presented. Finally, different photocatalytic applications of S‐scheme heterojunctions are summarized. Specifically, this work endeavors to clarify the critical understanding on curved Fermi level in S‐scheme heterojunction interface, which can help strengthen and advance the fundamental theories of photocatalysis. Moreover, the current challenges and prospects of the S‐scheme heterojunction photocatalyst are critically discussed.