[EN] Multilayer N-doped graphene photoelectrodes have been prepared following a straightforward one-step pyrolytic fabrication method. The N-doped graphene photoelectrodes have been demonstrated to work both as semitransparent electrodes and as efficient photoelectrocatalysts for H2 evolution at low bias. N-doped graphene photoelectrodes exhibited a constant H2 generation rate of 3.64 mmolh @1 cm2 at 0.2 V under 3443 Wm@2 irradiation for 17 h, reaching an applied-bias-compensated solar-to-hydrogen efficiency of 1.8%. The N-doped graphene photoelectrodes show light-intensity dependence as well as photocatalytic activity for H2 evolution in the UV/Vis spectral region. Impedance spectroscopy provides experimental evidence indicating that charge separation within N-doped graphene increases upon positive bias polarization of the photoelectrode. Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, Grapas and CTQ2015-69153-C02-R1) and Generalitat Valenciana (Prometeo 2013-014) is gratefully acknowledged. J.A. also thanks the Universitat Politecnica de Valencia for a postdoctoral scholarship. García-Gómez, A.; Albero-Sancho, J.; García Gómez, H. (2017). Multilayer N-doped graphene films as photoelectrodes for H2 evolution. ChemPhotoChem. 1(9):388-392. https://doi.org/10.1002/cptc.201700049