In this work we use hydrogen deposited molybdenum and tungsten oxides (chemically described as H:MOx x <= 3 where M = Mo or W) to control the energetics at the anode of bulk heterojunction (BHJ) organic photovoltaics (OPVs) based on poly(3-hexylthiophene):[6,6]-phenyl butyric acid methyl ester (P3HT:PC71 BM) blends. Significantly improved current densities and open circuit voltages were achieved as a result of improved hole transport from the P3HT highest occupied molecular orbital (HOMO) toward indium tin oxide (ITO) anode. This was attributed to the formation of shallow gap states in these oxides which are located just below the Fermi level and above the polymer HOMO and thus may act as a barrier-free path for the extraction of holes. Consequently, these states can be used for controlling the energetic structure of the anode of OPVs. By using ultraviolet photoelectron spectroscopy it was found that dependent on the deposition conditions these gap states and work function of the metal oxides may be tailored to contribute to the precise alignment of the HOMO of the organic semiconductor (OSC) with the Fermi level of the anode electrode resulting in further enhancement of the device performance. (C) 2014 Elsevier B.V. All rights reserved.