With the increasing issues of the energy crisis and environmental pollution, the development of clean energy has become an urgent task. Herein, self-supporting graphene (SSG) that could serve as the three-dimensional catalyst support is developed by electrochemically intercalating the flexible graphite paper (FGP) in 1 M KOH. Then, the Ni-base alloy is deposited on the SSG by electroless plating. The resulting electrode (Ni-Cu-P/SSG) exhibits excellent hydrogen evolution reaction (HER) electrocatalytic performance in 1 M KOH. The Ni-Cu-P/SSG catalyst just requires the overpotentials of 75 and 219 mV to reach 10 and 100 mA cm(-2), respectively. Besides, the Ni-Cu-P/SSG still maintains superior HER catalytic activity after the stability test of 12 h. The Ni-Cu-P/SSG composite catalyst with high catalytic activity, remarkable stability and facile preparation method has a significant influence on the extension of renewable energy preparation and application. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.