Solid polymer-blended electrolyte films of polyethylene oxide (PEO) + polyvinyl pyrrolidone (PVP)/lithium perchlorate embedded with iron (Fe) nanofiller in different concentrations have been synthesized by a solution casting method. The semicrystalline nature of these polymer electrolyte films has been confirmed from their XRD profiles. Polymer complex formation and ion–polymer interactions are systematically studied by FTIR and laser Raman spectral analysis. Surface morphological studies are carried out from SEM analysis. Dispersed Fe nanofiller size evaluation study has been carried out using transmission electron microscopy (TEM). In order to evaluate the thermal stability, decomposition temperature, and thermogravimetric dynamics, we carried out the TG/DTA measurement. Upon addition of Fe nanofiller to the PEO + PVP/Li⁺ electrolyte system, it was found to result in the enhancement of ionic conductivity. The maximum ionic conductivity has been set up to be 1.14 × 10⁻⁴ Scm⁻¹ at the optimized concentration of 4 wt% Fe nanofiller-embedded PEO + PVP/Li⁺ polymer electrolyte nanocomposite at an ambient temperature. PEO + PVP/Li⁺ + Fe nanofiller (4 wt%) cell exhibited better performance in terms of cell parameters. Based on the cell parameters, the 4 wt% Fe nanofiller-dispersed PEO + PVP/Li⁺ polymer electrolyte system could be suggested as a perspective candidate for solid-state battery applications.