A series of nanostructured catalysts based on cobalt-modified molybdenum carbides, intended as alternative replacement for platinum has been developed for the hydrogen evolution reaction (HER) from brine. The catalysts were synthesized by simple impregnation of the metal salts on carbon support and followed by pyrolysis in CH4 atmosphere. The obtained catalysts show impressive HER activities in both brine and alkaline media. At current density of -7.0 mA cm(-2), the overpotential for Co modified Mo/C catalysts was greater than that obtained with a commercial Pt/C catalyst by 63-89 mV and 15-148 mV for brine and alkaline solution, respectively. Our findings for HER in both media are consistent with electrochemical desorption of hydrogen gas following the Volmer-Heyrovsky mechanism as the rate-determining step. The HER activities of the catalysts were correlated to their high mesopore surface areas with active pores, nanocrystallites, and low charge transfer resistances as confirmed by electrochemical impedance spectroscopy. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.