Hydrogen peroxide (H2O2) synthesis generally requires substantial postreaction purification. Here, we report a direct electrosynthesis strategy that delivers separate hydrogen (H-2) and oxygen (O-2) streams to an anode and cathode separated by a porous solid electrolyte, wherein the electrochemically generated H+ and HO2- recombine to form pure aqueous H2O2 solutions. By optimizing a functionalized carbon black catalyst for two-electron oxygen reduction, we achieved >90% selectivity for pure H2O2 at current densities up to 200 milliamperes per square centimeter, which represents an H2O2 productivity of 3.4 millimoles per square centimeter per hour (3660 moles per kilogram of catalyst per hour). A wide range of concentrations of pure H2O2 solutions up to 20 weight % could be obtained by tuning the water flow rate through the solid electrolyte, and the catalyst retained activity and selectivity for 100 hours.