The development of gel polymer electrolytes (GPEs) for lithium-ion batteries (LIBs) has paved the way to powering futuristic technological applications such as hybrid electric vehicles and portable electronic devices. Despite their multiple advantages, non-aqueous liquid electrolytes (LEs) possess certain drawbacks, such as plasticizers with flammable ethers and esters, electrochemical instability, and fluctuations in the active voltage scale, which limit the safety and working span of the batteries. However, these shortcomings can be rectified using GPEs, which result in the enhancement of functional properties such as thermal, chemical, and mechanical stability; electrolyte uptake; and ionic conductivity. Thus, we report on PVDF-HFP/PMMA/PVAc-based GPEs comprising poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) and poly(methyl methacrylate) (PMMA) host polymers and poly(vinyl acetate) (PVAc) as a guest polymer. A physicochemical characterization of the polymer membrane with GPE was conducted, and the electrochemical performance of the NCM811/Li half-cell with GPE was evaluated. The GPE exhibited an ionic conductivity of 4.24 × 10⁻⁴ S cm⁻¹, and the NCM811/Li half-cell with GPE delivered an initial specific discharge capacity of 204 mAh g⁻¹ at a current rate of 0.1 C. The cells exhibited excellent cyclic performance with 88% capacity retention after 50 cycles. Thus, this study presents a promising strategy for maintaining capacity retention, safety, and stable cyclic performance in rechargeable LIBs.