In our research described herein, the hot pressing treatment at 90 °C under 2 tons of pressure on solution cast polymer nanocomposite (PNC) films based on a host matrix of poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) and poly(ethylene oxide) (PEO) with varying polymer blend compositions (20, 50, and 80 wt% P(VDF-HFP) or PEO) and 2 wt% zinc oxide (ZnO) nanofiller, was performed; the effects of this treatment and the composition variations on the optical, thermal, and dielectric properties was explored. The ultraviolet-visible wavelength range study revealed slightly reduced absorbance and a little increased energy band gap after the hot pressing of the nanocomposite films. Differential scanning calorimetry of the solution cast-hot pressed (SC-HP) PNC films explained the reduced thermal stability of the poly(ethylene oxide) crystallites and also the degree of crystallinity. The broadband dielectric measurements of these materials, at 27 °C, confirmed significant changes in various dielectric polarization processes, demonstrating a large redistribution of constituent interfaces by the hot press treatment. Additionally, the 90 °C hot pressed PNC film of equal polymer compositional ratio was further hot pressed at 130 °C and 160 °C, step by step, and characterized to examine the variations in dielectric properties. The properties of these thermally treated composite films are discussed concerning their use for flexible device applications.