Nanocomposite (NC) films of polyvinyl alcohol (PVA)/calcium aluminum-doped zincate (CaAl2ZnO5) have been fabricated with varying amounts, namely 2, 4, 6 and 8 wt% of CaAl(2)ZnO(5)nanoparticles (NPs) by solution casting technique. TEM data showed that an average particle size of CaAl(2)ZnO(5)NPs is ~ 25 nm. The effect of CaAl(2)ZnO(5)content on structural and morphological behaviors has been established by Fourier-transform infrared spectroscopy and scanning electron microscopy, respectively. The photo-response of NCs was derived by UV-visible spectroscopy where the band gap energy (E-g) reduced from 5.25 eV for PVA to 2.82 eV for PVA/8 wt% CaAl2ZnO5NC film. The dielectric permittivity and current-voltage (I-V) characteristics were studied using LCR-meter in frequency range of 50 Hz-5000 kHz. The relative dielectric constant (epsilon ') was increased from 15 to 65 with increase in NPs content from 0 to 8 wt%. The PVA NC with 8 wt% CaAl(2)ZnO(5)NPs raises the ac conductivity to 3.35 x 10(-5) S cm(-1)at room temperature. The cyclic voltammetry (CV) tests have been performed to calculate the specific capacitance of the NCs as a positive electrode against Ag/AgCl as reference electrode. The specific capacitance increases from 1. Fg(-1)for PVA to 3.69 Fg(-1)for PVA/8 wt% CaAl2ZnO5NC. These behaviors will support the possible applications in optical display devices and micro-electrical and electronic applications.