The present article deals with the preparation and characterization of pure and lead oxide (PbO) nanoparticles embedded polyvinyl alcohol (PVA) films by using a colloidal processing technique. PbO nanoparticles were successfully synthesized using the simple precipitation method. Polymer/ceramic-based flexible and self-standing films were obtained and further characterized using various analytical techniques. The mechanical and dielectric properties were also investigated. The Fourier Transform Infrared Spectroscopy (FTIR) results indicate that the structural characterization of PVA is strongly affected by the incorporation of PbO. Thermal analysis results indicate that the thermal stability of the PbO-doped PVA film has improved as compared with the neat PVA film. The mechanical property of nanocomposites has improved significantly due to an increase in filler loadings, indicating that a good interaction exists between PbO nanoparticles and PVA matrix. The dielectric constant of PVA/PbO nanocomposites has significantly improved with comparatively low dielectric loss values, indicating that the nanocomposites can be considered as an attractive material for embedded capacitor applications. © 2015 Wiley Periodicals, Inc.