The development of cost-effective cathodes, operating at neutral pH and ambient temperatures, is a crucial challenge for the practical application of microbial electrolysis cell (MEC) technology. In this study, NiW and NiMo co-deposits produced by electroplating on Ni-foam are explored as cathodes in MEC. The fabricated electrodes exhibit higher corrosion stability and enhanced electrocatalytic activity towards hydrogen evolution reaction in neutral electrolyte compared to the bare Ni-foam. NiW/Ni-foam electrodes possess six times higher intrinsic catalytic activity, estimated from data obtained by linear voltammetry and chronoamperometry. The newly developed electrodes are applied as cathodes in single-chamber membrane-free MEC reactors, inoculated with wastewater and activated sludge from a municipal wastewater treatment plant. Cathodic hydrogen recovery of 79% and 89% by using NiW and NiMo cathodes, respectively, is achieved at applied voltage of 0.6 V. The obtained results reveal potential for practical application of used catalysts in MEC. (C) 2017 Elsevier B.V. All rights reserved.