Amorphous rhenium nanoparticles modified silicon nanowires were prepared via reducing Re ion by Si-H bonds, which were employed to electrocatalysize the hydrogen evolution reaction because amorphous structure may have excellent catalytic activity. It is interesting that an obvious self-activation for Re/Si catalysts was observed with the current density enhanced by 2.2 times its previous value at 400 mV after a 3,000 s of continuous cyclic voltammetry scanning, and the catalytic performance remained steady thereafter. The optimal electrocatalytic performance was found with the Re: Si mass ratio of 31.1:68.9, resulting in a Tafel slope of 81 mV.dec(-1) and overpotential of 100 mV at current density of 10 mA.cm(-2). (C) 2017 Elsevier Ltd. All rights reserved.