Nowadays, metal-oxides impregnated conducting polymers as electrode materials are attracted much attention due to their higher stability. Here, the metal-oxide cluster, polyoxometalate (K5H2[PV4W8O40]·11H2O, PV4W8), was introduced into the polypyrrole (PPy) matrix to overcome the polymers stability issues, and thus, the resulting novel PV4W8/PPy (symmetric) composite electrode has been reported. XPS confirmed the presence of all atoms on the polymer backbone with respective oxidation states. Nevertheless, doping of PV4W8 on the conductive PPy matrix's surface can affectively improve the ion's transfer. Finally, the asymmetric PV4W8-PPy/PPy composite exhibits a prodigious specific capacitance of 291 F g−1, larger than the PPy (90.01 F g−1) and PV4W8 (39.03 F g−1) at 0.4 A g−1 current density. The PV4W8-PPy/PPy (asymmetric) electrode showed excellent cycle stability. However, a symmetric supercapacitor device based on PV4W8/PPy composite possesses a specific capacitance of 195.27 F g−1 and an energy density of 8.94 Wh kg−1 at the same current density as PV4W8-PPy/PPy (asymmetric) electrode with remarkable cycle stability. © 2021 Elsevier B.V.