Recently, step‐scheme (S‐scheme) photocatalysts have received widespread attention in the field of solar fuel development and transformation because of efficient charge spatial separation along with strong redox capabilities. Herein, the development history of S‐scheme photocatalysts is summarized and reviewed, from Z‐scheme photocatalysts to S‐scheme photocatalysts. Advantages of S‐scheme photocatalysts are also discussed in depth and detail, including design principles and construction strategies as well as charge transfer mechanisms. In addition, identification characterizations for S‐scheme photocatalysts and their solar energy conversion applications are also reviewed. Finally, conclusions and outlooks for solar energy conversion challenges are demonstrated. It provides insights and up‐to‐date information to enable the scientific community to fully tap into the potential of S‐scheme photocatalysts in renewable energy generation and environmental remediation.

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