Composite films of Polyvinyl alcohol (PVA) mixed with Lead Titante Oxide (PbTiO3) were prepared. Dopant incorporated and DC bias induced electrical parameters were disclosed with respect to pure PVA film. The results demonstrate dielectric polarization is not only directly proportional to PbTiO3% of dopant but also external DC bias potential at 30 °C based on Maxwell Wagner theory. Hence these properties highly applicable as super-capacitor film and humidity sensor applications. © 2011 Elsevier B.V. All rights reserved.