<p>Hydrogen peroxide (H₂O₂) is widely used in household and industrial applications but its synthesis is energy-intensive. An alternative to the traditional anthraquinone process is H₂O₂ electrosynthesis through a two-electron oxygen-reduction reaction (2e^– ORR), using a membrane electrode assembly (MEA). In this Review, we overview the use of the MEA configuration for H₂O₂ electrosynthesis. A typical MEA cell includes a gas-diffusion electrode, an ion-exchange membrane and a flow field plate that regulate the mass transport of O₂, water (reactant) and H₂O₂ (product) and manage the liquid–gas interactions. Depending on the ion-exchange membrane used, the H₂O₂ electrosynthesis systems are classified as single-membrane MEA, double-membrane solid-electrolyte MEA and membrane-free. Reducing the cell voltage or increasing the yield can be achieved through anode design strategies, including organic upgrading with low electro-oxidation potential and two-electron water oxidation that enables a theoretical full-cell H₂O₂ Faradaic efficiency of 200%. MEA-based H₂O₂ electrosynthesis coupled with downstream thermocatalytic chemical synthesis can produce value-added chemicals such as alcohols and epoxides. Current H₂O₂ electrosynthesis is approaching industrially relevant current densities (&gt;300 mA cm^–2), but long-term stability across diverse electrolysis environments (such as different pH conditions) requires optimization to meet the requirements of commercial applications.</p>