Background Developing a green chemical production pathway driven by electricity and capable of being coupled with renewable energy is an important approach to achieving carbon-neutral energy conversion. Hydrogen peroxide (H₂O₂), as a mild oxidant and energy storage medium, has wide-ranging applications in environmental protection and energy conversion. However, the current industrial production of H₂O₂ faces issues such as high energy consumption and transportation risks. The electrochemical oxygen reduction reaction via the two-electron pathway (2e⁻ ORR) provides a new technical solution for the green synthesis of H₂O₂. Using oxygen and water as raw materials, H₂O₂ can be directly generated under an applied potential at ambient temperature and pressure, overcoming the limitations of the traditional anthraquinone method and offering unique advantages in advanced oxidation and green chemical processes. Challenges Nevertheless, the practical deployment of electrochemical H₂O₂ synthesis is currently hindered by several key challenges, including insufficient selectivity toward the 2e⁻ pathway, high overpotentials, poor long-term catalyst stability, and difficulties in scaling up production while maintaining high H₂O₂ concentrations. Mechanisms and Materials This review systematically elucidates the mechanisms underlying the selective electrochemical reduction of oxygen to H₂O₂ and clarifies the feasibility of regulating the number of electron transfers and enhancing reaction selectivity through microenvironment regulation. By summarizing the effects of different electrode materials on oxygen reduction efficiency and selective H₂O₂ production, this review provides important insights for further material development and process optimization. Among them, noble-metal electrodes (e.g., Au, Pt, and Ag) and carbon-based electrodes modified through doping or defect engineering promote H₂O₂ production by tuning the adsorption or desorption behavior of the *OOH intermediate. Specific material categories are further discussed in detail, including noble metal alloys (such as Pt-Hg and Pd-Hg), which can significantly inhibit the cleavage of the O–O bond and improve the selectivity for H₂O₂. Carbon-based materials (such as those doped with heteroatoms or metal atoms, or engineered with defects) possess tunable electronic structures and oxygen-containing functional groups that are conducive to the formation of *OOH. Simultaneously, regulating the pore structure of carbon-based materials enables control of the local reaction microenvironment, thereby achieving excellent activity and selectivity in the 2e⁻ ORR process. Furthermore, this review clarifies the influence of different reactor configurations on mass transfer during the ORR process. Perspectives Finally, this review briefly presents cases of integrating the electrochemical oxygen reduction system with in situ green chemical synthesis, summarizes the critical challenges currently faced by electrochemical H₂O₂ production technology, and outlines promising directions for future development.