Microbial electrolysis cells (MECs) provide an innovative bioelectrochemical approach for hydrogen production using microorganisms as biocatalysts. The development of cost-effective cathodes for near-neutral pH and ambient temperature conditions is the most critical challenge for the practical application of MEC technology. In this study, the electrocatalytic properties of electrodeposited onto carbon felt NiFe-, NiFeP- and NiFeCoP-nanostructures towards HER in neutral and weak acidic solutions were investigated. The voltage needed to initiate hydrogen production and the current production rates were estimated from obtained linear voltammograms. The developed composite materials possess much higher catalytic activity than bare carbon felt. The highest current production rate corresponding to 1.7 +/- 0.1 m(3)H(2)/day/m(2) was achieved with NiFeCoP/carbon felt electrodes. In addition, the applied modifications result in improvement of the corrosion resistance. The obtained results demonstrate that Ni-based nanomodified materials are promising electrocatalysts for HER in near-neutral electrolytes and could be applied as cathodes in MECs. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.