This research paper aims to fabricate flexible PVA/Cs/TiO2 nanocomposite films consisting of polyvinyl alcohol (PVA), chitosan (Cs), and titanium oxide (TiO2) for application in energy storage devices. The samples were analyzed using X-ray diffraction (XRD), atomic force microscope (AFM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and energy dispersive X-ray (EDX) techniques. The impact of TiO2 on the electrical impedance, conductivity, permittivity, and energy efficiency of the PVA/Cs was determined in a frequency range of 100 Hz to 5 GHz. The XRD, FTIR, and EDX results showed the successful fabrications of the PVA/Cs/TiO2. The SEM and AFM images illustrated that the TiO2 was loaded and distributed homogenously in PVA/Cs chains. In addition, the electrical conductivity was enhanced from 0.04 × 10−7 S.cm−1 of PVA/Cs to 0.25 × 10−7 S.cm−1 and 5.75 × 10−7 S.cm−1, respectively, for the composite PVA/Cs/0.01TiO2 and PVA/Cs/0.1TiO2, and the dielectric constant grew from 2.46 for PVA/Cs to 7.38 and 11.93, respectively. These results revealed that modifications were made to the produced films, paving the way for using the composite PVA/Cs/TiO2 films in different energy applications, such as electronic circuits and supercapacitors.