Blended nanocomposite solid polymer electrolytes are gaining considerable attention as next-generation materials for use in flexible lithium-ion battery systems. These materials help ensure a more uniform distribution of lithium ions at the electrode–electrolyte interface, contributing to the development of a stable interfacial layer that mitigates lithium dendrite formation. In this study, solid polymer electrolytes were synthesized using a binary polymer matrix composed of polyethylene oxide (PEO) and polymethyl methacrylate (PMMA), with lithium iodide (LiI) as the ionic salt. Zirconium dioxide (ZrO₂) nanoparticles were introduced as nanofillers in varying concentrations to investigate their influence on the physical and functional characteristics of the polymer matrix. Characterization was carried out using Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), and X-ray Diffraction (XRD). SEM images indicated that ZrO₂ nanoparticles remained well-dispersed up to 3 wt%, while higher loadings showed slight agglomeration. FTIR analysis revealed noticeable changes in absorption bands, suggesting strong interactions among polymer chains and the nanofillers. XRD data confirmed the semi-crystalline behaviour of the PEO/PMMA blend system. The inclusion of ZrO₂ nanofillers enhanced the structural integrity and ionic conductivity of the polymer matrix, making it as promising candidates for applications in electrochemical energy storage and advanced material interfaces. The systematic incorporation of ZrO₂ nanofillers into the PEO/PMMA matrix significantly improved the microstructural uniformity, polymer–filler interactions, and ionic transport behaviour of the solid polymer electrolytes.