In the present exploration, MXene (Ti 3 C 2 T x ) based composite polymer electrolytes (CPEs) are fabricated by electrospinning technique to make free-standing fiber films. In this process, four different composite polymer electrolytes (CPEs) are synthesized by varying the MXene content from 0 mg to 60 mg in poly-acrylonitrile (PAN) along with NaPF 6 solution. The electron microscopic studies reveal the layered morphology of synthesized MXene samples. Further, MXene based CPE fibers exhibit lengths of several micro-meters with widths < 3 μm. The linear sweep voltammetry results manifest the electrochemical stability of CPE S up to 3.3 V. The key studies in this research work are the incorporation of sodium-based salts which are more abundant, less expensive, less reactive, and environment friendly than other Li based salts, also the highlighted findings have been assigned to the impedance and the DC polarization, which illustrate the enhanced ionic conductivities (of the order of 10 À 6 S/cm) for the 20 mg MXene based CPE sample. Further, the Fourier Transform Infra-Red (FTIR) spectroscopy analysis and its deconvolution studies have been carried out, which depict the enhancement in the free ion concentration in the MXene based CPEs samples.