Interfacial electron-transfer (ET) reactions underpin the interconversion of electrical and chemical energy. It is known that the electronic state of electrodes strongly influences ET rates because of differences in the electronic density of states (DOS) across metals, semimetals, and semiconductors. Here, by controlling interlayer twists in well-defined trilayer graphene moirés, we show that ET rates are strikingly dependent on electronic localization in each atomic layer and not the overall DOS. The large degree of tunability inherent to moiré electrodes leads to local ET kinetics that range over 3 orders of magnitude across different constructions of only three atomic layers, even exceeding rates at bulk metals. Our results demonstrate that beyond the ensemble DOS, electronic localization is critical in facilitating interfacial ET, with implications for understanding the origin of high interfacial reactivity typically exhibited by defects at electrode-electrolyte interfaces.