Electrocatalytic hydrogen evolution reaction, the cornerstone of the emerging hydrogen economy, can be essentially facilitated by robustly heterostructural electrocatalysts. Herein, we report a highly active and stably heterostructural electrocatalyst consisting of NiCoP nanowires decorated with CoP nanoparticles on a nickel foam (NiCoP-CoP/NF) for effective hydrogen evolution. The CoP nanoparticles are strongly interfaced with NiCoP nanowires producing abundant electrocatalytically active sites. Combined with the integrated catalyst design, NiCoP-CoP/NF affords a remarkable hydrogen evolution performance in terms of high activity, enhanced kinetics, and outstanding durability in an alkaline electrolyte, superior to most of the Co (or Ni)-phosphide-based catalysts reported previously. Density functional theory calculations demonstrate that there is an interfacial effect between NiCoP and CoP, which allows a preferable hydrogen adsorption and thus contributes to the significantly enhanced performance. Furthermore, an electrolyzer employing NiCoP-CoP/NF as the cathode and RuO2/NF as the anode (NiCoP-CoP/NF||RuO2/NF) exhibits excellent water-splitting activity and outstanding durability, which is comparable to that of the benchmark Pt-C/NF||RuO2/NF electrolyzer.