Transition metal phosphides (TMPs) have been received widespread research attention and developed as electrode materials for their superior electrical conductivity and excellent redox activity. In this work, self-supported three-dimensional hierarchical core-shell NiCoP@NiCoP@CC electrode has been fabricated by a two-step hydrothermal and a phosphorization method, in which NiCoP@NiCoP core-shell leaf-like arrays are directly grown on carbon cloth. The electrode integrates the advantages of the 1D core for “hyperchannel” of the electron transport, 2D shell on core for a short diffusion distance for the ions and also the charge carrier meanwhile improvement of cycle stability, and 3D networked substrate for flexibility. The as-fabricated electrode shows superior electrochemical performance and delivers a high specific capacity of 1125 C g−1 (312 mAh g−1) at 1 A g−1, and outstanding rate capability with 78.0% retention even at 10 A g−1 and still retain 808 C g−1 (224 mAh g−1) (71.8% retention) after 2000 cycles. In addition, the asymmetric supercapacitor has also been assembled for actual use by employing NiCoP@NiCoP electrode as the anode and the activated carbon (AC) as the cathode, which displays a voltage window of 1.5 V and a high energy density of 34.8 Wh kg−1 at a power density of 750.0 W kg−1. The results demonstrate feasibility of NiCoP@NiCoP core-shell array on carbon cloth as electrode material for high performance hybrid supercapacitor applications.