Photocatalysis opens a new door to H2O2 formation via a low-cost, clean, mild, and sustainable process, which holds great promise for the next generation of massive H2O2 production. However, fast photogenerated electron–hole recombination and slow reaction kinetics are the main obstacles for its practical application. An effective solution is to construct the step-scheme (S-scheme) heterojunction, which remarkably promotes carrier separation and boosts the redox power for efficient photocatalytic H2O2 production. Considering the superiority of S-scheme heterojunctions, this Perspective summarizes the recent advances of S-scheme photocatalysts for H2O2 production, including photocatalysts for building S-scheme heterojunctions, H2O2-production performance, and S-scheme photocatalytic mechanisms. Lastly, some prospects are given to motivate future research in this promising field, other promising strategies are provided to further improve H2O2 yields, and future research directions are suggested.