Recently, researchers have shown increasing interest in transition metal phosphides (TMPs) for their outstanding performance on electrochemical energy storage. Herein, we take a simple hydrothermal route to prepare NiCoP/Co (OH)2 nanoarrays. The constructing of 3D hierarchical core-shell structure endows the material with enlarged contact area, reduced ion diffusion distance and better mechanical stability. Therefore, NiCoP/Co (OH)2 electrode combining NiCoP with high electrochemical activity and Co (OH)2 with superior stability exhibits remarkable electrochemical performance with specific capacity of 304 mAh g−1 at 1 A g−1 and retains 80% of the initial capacity at 20 A g−1. Furthermore, the as-fabricated asymmetric supercapacitors display outstanding long-term cycle life with 87% retention after 6000 cycles at 10 A g−1 and high energy density/power density. The above results suggest that the NiCoP/Co (OH)2 electrode holds considerable application potential for hybrid supercapacitors.