Polyvinyl alcohol (PVA)-composed lead oxide (PbO) films were prepared by solution casting method. Proposed composite moiety reveals the presence of orthorhombic and monoclinic multiphase structural modification due to loading of PbO which was demonstrated by X-ray diffraction. The electronic transition due to oxide impurity decreases the transmission intensity and shift of wavelength confirmed by ultraviolet tool. The magnitude of dielectric polarization is directly proportional to the loaded PbO% and is based on the Debye model. The composite morphology demonstrates the presence of inorganic filler with a cross linked network of polymer PVA confirmed by AFM. The synthetic film loaded with PbO sensing for varying RH% with linearity (decreasing) in resistance may apply as humidity sensor.