Nano-Ni0.5Zn0.5Fe2O4 embeded in polyvinyl alcohol (PVA) with different weight ratios (5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 30 wt.%, 40 wt.% and 50 wt.%) were prepared by solution casting. The formation of PVA/Ni0.5Zn0.5Fe2O4 hyprid composite is confirmed through x-ray diffraction, scanning electron micrographs, transmission electron microscopy, and Fourier transform infrared spectroscopy analysis. Thermogravimetric analysis showed that the composite films have thermal stability higher than pure PVA. The complex dielectric constant (e*), electrical conductivity, electric modulus and impedance spectra of these polymer nanocompsites have been studied over the frequency range 1 Hz–20 MHz. The real permittivity (e′) of PVA polymer film enhanced while the real electric modulus (M′) decreased by the addition of Ni0.5Zn0.5Fe2O4 nanoparticles. The imaginary part of permittivity has the same trendline of e′ leading to the increase in its values. These aspects of PVA composites making it a promising material to be used in microwave absorbers depending on the dielectric loss.