Qikai Shentu, Kewen Xing, Keliang Li, Na Han, Yanguang Li
Abstract Hydrogen peroxide (H 2 O 2 ) is a widely used green oxidant in industrial, environmental, and medical applications, yet its conventional anthraquinone‐based production is energy‐intensive, centralized, and environmentally taxing. Electrochemical H 2 O 2 synthesis via the two‐electron oxygen reduction reaction (2e ORR) and the two‐electron water oxidation reaction (2e WOR) offers a sustainable and decentralized alternative that enables on‐site generation under mild conditions. Realizing efficient and scalable H 2 O 2 production requires the development of electrocatalysts and systems that deliver high selectivity, activity, and stability. In this review, a comprehensive summary of recent advances in electrochemical H 2 O 2 generation is provided, with a focus on strategies to enhance selectivity. The fundamental reaction mechanisms and analytical techniques used to quantify H 2 O 2 are first discussed. Recent progress across three critical areas: catalytic material design, regulation of the interfacial microenvironment, and optimization of electrolyzer configurations, is then discussed. Finally, key challenges that currently hinder large‐scale implementation and outline future research directions to advance the development of practical H 2 O 2 electrosynthesis technologies for industrial and environmental applications are identified.