Nanocomposite polymer electrolyte membranes (NCPEMs) based on poly(acrylic acid)(PAA) and titania (TiO₂) are prepared by a solution casting technique. The ionic conductivity of NCPEMs increases with the weight ratio of TiO₂.The highest ionic conductivity of (8.36 ± 0.01) × 10⁻⁴ S·cm⁻¹ is obtained with addition of 6 wt % of TiO₂ at ambient temperature. The complexation between PAA, LiTFSI and TiO₂ is discussed in Attenuated total reflectance-Fourier Transform Infrared (ATR-FTIR) studies. Electrical double layer capacitors (EDLCs) are fabricated using the filler-free polymer electrolyte or the most conducting NCPEM and carbon-based electrodes. The electrochemical performances of fabricated EDLCs are studied through cyclic voltammetry (CV) and galvanostatic charge-discharge studies. EDLC comprising NCPEM shows the specific capacitance of 28.56 F·g⁻¹ (or equivalent to 29.54 mF·cm⁻²) with excellent electrochemical stability.