LAUSR

Hydrogen peroxide (H2O2) as a green oxidizing agent is widely used in various fields. Electrosynthesis of H2O2 has gradually become a hotspot due to its convenient and environment‐friendly features. Single‐atom‐site catalysts (SASCs) with uniform active sites are the ideal catalysts for the in‐depth study of the reaction mechanism and structure‐performance relationship. In this review, the outstanding achievements of SASCs in the electrosynthesis of H2O2 through 2e− oxygen reduction reaction (ORR) and 2e− water oxygen reaction (WOR) in recent years, are summarized. First, the elementary steps of the two pathways and the roles of key intermediates (*OOH and *OH) in the reactions are systematically discussed. Next, the influence of the size effect, electronic structure regulation, the support/interfacial effect, the optimization of coordination microenvironments, and the SASCs‐derived catalysts applied in 2e− ORR are systematically analyzed. Besides, the developments of SASCs in 2e− WOR are also overviewed. Finally, the research progress of H2O2 electrosynthesis on SASCs is concluded, and an outlook on the rational design of SASCs is presented in conjunction with the design strategies and characterization techniques.