Rh-Fe nanoparticles (NPs) with variable Rh/Fe ratios have been obtained by direct current electrodeposition onto Au-metalized Si/Ti substrates from an electrolyte containing Rh(III) and Fe(III) chloride salts. NP mean diameter could be varied in the range of 20-80 nm by playing with the applied current density (-j = 0.5-2 mA cm(-2)) and deposition times (t = 200-3200 s). NPs were very well adhered to the substrate and became progressively enriched in Fe as the absolute value of the current density increased. X-ray photoelectron spectroscopy analyses revealed that the NPs are mostly metallic. The oxygen signal detected at surface level is relatively high but reduces down to less than 1 at% after 1 min Ar ions sputtering. The as-deposited Rh-Fe NPs are active toward hydrogen evolution reaction in alkaline medium. Different values of the onset potential for water reduction have been observed depending on the j and t values applied for NPs growth. Cycling stability tests reveal that NPs do not suffer from excessive deterioration of their electrocatalytic activity with time. (C) 2016 Elsevier Ltd. All rights reserved.