Nano-sized Ni3P2O8-Co3P2O8·8H2O is synthesized via a facile chemical precipitation method as the active material of supercapacitors. The experiment result expresses the Ni3P2O8-Co3P2O8·8H2O of the Ni/Co molar ratio of 8:2 exhibits enhanced capacitive behaviors relatively than others, it delivers a highest mass specific capacitance of 1974Fg−1 at 0.5Ag−1, which is higher than both Ni3P2O8 and Co3P2O8·8H2O. The sforzato in specific capacitance is on account of the pore structure, uniform particle morphology, and hyperbaric of Ni. An asymmetric supercapacitor is assembled using the Ni3P2O8-Co3P2O8·8H2O and activated carbon (AC) as positive and negative electrode, respectively. It not only sends a large specific capacitance (94Fg−1) but also good cycling stability (up to 5000 cycles). The impressive results presented here may be potential applications for high energy density storage systems.