A mixture of graphene/graphite as new support was prepared by ball milling procedure and was used for Nickel nanoparticles supported that was employed as a cathode catalyst for hydrogen evolution reaction (HER) in the KOH solution. The structure and electrocatalytic activity of electrocatalyst were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) analysis, and electrochemical techniques. The results indicated that by raising the time of the ball milling from 0 to 270 min, the HER activity of electrocatalyst first increased, and then decreased according to the increase of active sites and then agglomeration of Ni nanoparticles. Ni nanoparticles supported on the mixture with 180 min ball milling exhibited the highest HER activity with a low overpotential (205 mV at 10 mA cm(-2)), Tafel slope of 84 mV dec(-1), and remarkable durability. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.