Highly efficient and stable organic photovoltaic (OPV) cells are demonstrated by incorporating solution-processed hydrogen molybdenum bronzes as anode interlayers. The bronzes are synthesized using a sol-gel method with the critical step being the partial oxide reduction/hydrogenation using an alcohol-based solvent. Their composition, stoichiometry, and electronic properties strongly correlate with the annealing process to which the films are subjected after spin coating. Hydrogen molybdenum bronzes with moderate degree of reduction are found to be highly advantageous when used as anode interlayers in OPVs, as they maintain a high work function similar to the fully stoichiometric metal oxide, whereas they exhibit a high density of occupied gap states, which are beneficial for charge transport. Enhanced short-circuit current, open-circuit voltage and, fill factor, relative to reference devices incorporating either PEDOT-PSS or a solution processed stoichiometric molybdenum oxide, are obtained for a variety of bulk heterojunction mixtures based on different polymeric donors and fullerene acceptors. In particular, high power conversion efficiencies are obtained in devices that employed the s-HxMoO2.75 as the hole extraction layer.