In this work, the cast solutions manufacturing approach was applied to prepare a PVA/TiO2 composite, which is made of titanium dioxide (TiO2) and polyvinyl alcohol (PVA). The energy dispersive X-ray (EDX), atomic force microscope (AFM), and Fourier transform infrared (FTIR) methods were employed to indicated the successful preparations of the composites. Moreover, the XRD and SEM methodologies were employed to investigate the impact of ion bombardment on the structural characteristics and surface morphology of the composite PVA/TiO2. The prepared films were irradiated with oxygen beam at fluencies; 0.3 × 1017, 0.6 × 1017, and 0.9 × 1017 ions cm−2. The ion beam increases the surface roughness of the PVA/TiO2 from 17 nm for the un-bombarded up to 25 nm for highly irradiated one, as indicated and measured by AFM images. The dielectric behavior of the pure and bombarded films were measured at the frequency of 50 Hz-6 MHz. The results reveal that the dielectric properties of PVA/TiO2 films were significantly modified by the oxygen beam bombardment. The results of the research pave the way for potential applications of irradiated PVA/TiO2 nanocomposite sheets in various forms of energy storage as capacitors and batteries.