Hydrogen production in microbial electrolysis cells (MECs) is a promising approach for energy harvesting from wastewater. The kinetic barriers toward proton reduction necessitate the use of catalysts to drive hydrogen formation at appreciable rates and low applied potentials. Towards this end, cost effective alternatives to platinum catalysts are of paramount interest. In this study, Ni(OH)(2) films were synthesized by electrophoretic deposition from a Ni(II) cyclam precursor solution at varying concentrations (6 mM, 15 mM, and 23 mM). The films were characterized by scanning electron microscopy and X-ray photo-electron spectroscopy to confirm the deposition of Ni(OH)(2). The Ni(OH)(2)-modified electrodes were then examined by both traditional electrochemical measurements and in an MEC for hydrogen production. Tafel analysis indicates an exchange current density of similar to 0.36 mA cm(-2) with a Tafel slope of similar to 120 mV decade(-1) consistent with a rate determining proton adsoprtion step. The hydrogen production rates increased with increasing Ni(II) cyclam concentration in the precursor solution, with the 23 mM-derived film exhibiting a rate comparable to that of a Pt-based catalyst in MEC tests. (C) The Author(s) 2016. Published by ECS. All rights reserved.