Considering the synergistic effect of transition metal phosphides and 3D structure substrates, herein, we directly deposited well-defined hierarchical radial NixP nanospheres on Ni foam via a facile, one-step co-electrochemical method to function as highly active flexible electrodes for both hydrogen evolution reaction and supercapacitor. Impressively, the bifunctional NixP/NF electrode requires an overpotential of only 63 mV to achieve a current density of 10 mA cm(-2) and demonstrates a low Tafel slop of 55 mV dec(-1) in 1 M KOH. Moreover, the electrochemical supercapacitor based on this hierarchical NixP/NF electrode also shows a superior specific capacitance of 1684 mF cm(-2) (382.7 F/g) at a current density of 2 mA cm(-2) and an outstanding retention ratio of 110.9% of its original capacitance value after 4000 cycles in 6M KOH. Hopefully, excellent electrochemical performances demonstrate that this NixP/NF material could be a promising candidate for future applications in both hydrogen evolution reactions and supercapacitors.