Nanocomposite membranes of ZrO2 doped polyvinyl alcohol (PVA) with varying amounts of ZrO2 nanoparticles (5, 9, and 13 wt %) have been prepared via a solution casting technique. ZrO2 nanoparticles using as a filler synthesized by sol‐gel technique. Effects of ZrO2 nanoparticles doping on composites morphological, optical, luminescence and structural, characteristics has been analyzed using atomic force microscopy (AFM), X‐ray diffraction (XRD), UV‐visible spectroscopy, photoluminescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), X‐ray photon electron spectroscopy (XPS) and Field emission scanning electron microscopy (FESEM). The XRD studies confirmed the successful incorporation of ZrO2 into the PVA matrix and showed improved crystallinity following doping of ZrO2 in PVA. The average size of ZrO2 nanoparticles calculated by XRD agreed well with the particles size measured by the TEM. UV‐visible studies of nanocomposite membranes show the enhancement in absorption intensity and slight red shift in peak positions as the ZrO2 concentration increases. The enhancement in absorption intensity suggests the potential applications in filters and solar cells. The maximum PL intensity was observed for 5 wt % of ZrO2 in PVA/ZrO2 composite membrane suggested that this concentration is most suitable for optoelectronic applications.This article is protected by copyright. All rights reserved.