Ground-breaking research into the development of a multilayer composite polymer electrolyte aims to enhance the safety associated with liquid electrolytes utilized in lithium batteries. The electrolyte consists of two outer layers made of electrospun poly(vinylidene fluoride) (PVDF) and a middle layer comprised of a fibrous membrane containing PEO, PAN-PEO, PEO-NbO2, and PAN-PEO-NbO2. The investigated PEO-PAN-NbO2 system demonstrates a higher room temperature ionic conductivity of 2.451 × 10−1 mS cm−1 than that of single-phase electrolyte systems. Incorporating inorganic fillers such as NbO2 into PEO polymer electrolytes, in conjunction with PAN copolymerization, significantly enhances ionic conductivity and amplifies surface area. Consequently, the utilization of these techniques that demonstrate increased polymer membranes leads to improved efficiency and security of solid-state electrochemical devices. The multilayer composite polymer electrolyte is created by continuous electrospinning, which allows for precise control and improves safety features.