Herein, the interfacial polymerization method has been used for the synthesis of PPy/NaVO3 composites with different compositions of NaVO3 (10 %, 20 %, 30 %, 40 % and 50 %) as an efficient electrode material for supercapacitors. The successful formation and composition of the as-prepared composites (PV1-PV5) were confirmed by FTIR, XRD, EDX, and SEM analysis. The electrochemical properties were investigated by cyclic voltammetry (CV), galvanometric charge–discharge measurement (GCD), and electrochemical impedance spectroscopy (EIS) in 0.5 M H2SO4 electrolyte. As compared to other, the PV4 composite exhibit excellent specific capacitance of 391 F g−1 at a current density of 0.75 A/g with good cycling stability of ∼59 % after 1000 cycles. Furthermore, the PV4 composite also shows a high specific energy density of 14 Wh kg−1 and a specific power density of 150 W kg−1. The excellent electrochemical performance of PPy/NaVO3 composites (PV1-PV5) was attributed to the synergistic effect of conducting PPy and NaVO3 which provides the effective surface area for the efficient storage of ions and transfer of electrons and ions on the surface of the electrode. Thus, these excellent electrochemical performances reflect and suggest the practical application of PV4 electrode material for future high-energy–density supercapacitors.