A comparative study of an O2-diffusion cathode and a H2-diffusion anode has been performed to ascertain the limiting processes, when they are combined in a flow alkaline fuel cell with hydroperoxide ion generation. The linear sweep voltammograms and the impedance diagrams of both electrodes show large differences. The cathode reaction is charge transfer-controlled up to current densities of at least 1 A cm−2, whereas the dissociative adsorption, charge transfer and diffusion of H2 appear to limit the anode reaction. The anode, with limiting current densities of about 90 and 150 mA cm−2 for 1.0 and 6.0 M KOH, respectively, then clearly controls the hydroperoxide ion production in the fuel cell. Diffuse reflectance infrared Fourier transform spectroscopy and X-ray photoelectron spectroscopy reveal that, the carbon of the H2-diffusion anode does not undergo significant oxygen functionalisation during hydroperoxide ion generation in the fuel cell.