Present work, ZrO2/CuO/PVA (ZC-PVA), ZrO2/Fe2O3/PVA (ZF-PVA) and ZrO2/CuO/Fe2O3/PVA (ZCF-PVA) nanofibers were synthesized by cost effective electrospinning method. The ZCF-PVA nanofiber prepared in this study were subjected to analysis using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS) techniques, individually. XRD was employed to ascertain both the structure and crystallite size of the synthesized materials. SEM and FT-IR analysis were used to identify the morphology and functional groups present in the prepared ZC-PVA, ZF-PVA and ZCF-PVA nanofibers. XPS confirmed the surface elemental composition and oxidation states of Zr4+, Cu2+, and Fe3+ in ZCF-PVA nanofiber comprising ZrO2, CuO, and α-Fe2O3. In three electrode configuration ZCF-PVA nanofiber shows significantly higher specific capacitance of 824 F/g at 1 A/g current density under 1 M KOH. The generation of synergic effect between multi valence oxidation states of mixed metal oxides and polymer (ZCF-PVA) enhances the capacitive behavior. The ZCF-PVA symmetric device exhibits 184 F/g at 0.5 A/g current density with 91 % capacitance retention and 94 % of coulombic efficiency even after 5000 cycles at 3 A/g of current density. © 2024 Elsevier B.V., All rights reserved.