Nickel phosphide-based nanomaterials have been acted as efficient catalysts for the hydrogen evolution reaction (HER), however, the design of novel and high performance HER catalyst is still a challenge. Herein, we report a novel 2D material black phosphorus (BP) as support for constructing Ni2P-based hybrid catalyst by a one-pot thermal decomposition approach. TEM results indicated that the monodispersed Ni2P nanoparticles with small size and good dispersion supported on the surface of layered BP, which implied that more catalytic active sites may be exposed for HER. The as-synthesized Ni2P/BP hybrid exhibits high HER electrocatalytic performance with low onset overpotential (70 mV), small Tafel slope (81 mV dec(-1)), large double-layer capacitance (1.24 mF cm(-2)), high conductivity and good stability, which can be assigned to the strong synergistic effect between Ni2P and BP. Therefore, BP may be a suitable support for constructing excellent catalysts in electrocatalysis. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.