These works validate the efficacy of S-scheme heterojunction photocatalysts in integrating H₂ generation and organic synthesis. Meanwhile, the synergetic employment of various in situ characterization methods in the exploration of S-scheme photocatalytic mechanism is exemplified. The development of versatile heterojunction photocatalysts will be inaugurated. In future works, S-scheme photocatalysts are expected to achieve more combination of various redox reactions, such as H₂O₂ production coupled with organic synthesis, and Cr(VI) reduction hybridized with pollutant degradation. Besides, employing cocatalysts to decorate S-scheme heterojunctions can further boost the photocatalytic activity by accelerating charge separation and facilitating molecule adsorption.