The PEO/PVP polymers blend films at different wt % of PVP are prepared by solution casting method using methanol as a solvent. The samples were characterized by FT-IR to confirm the complexation between the two polymers and the peak region around 1230–980 cm−1 corresponds to C–O–C symmetric and asymmetric stretchings and changes in band positions was observed in PEO/PVP polymer blend. The Field Emission Scanning Electron Microscope (FESEM) images shows morphology changes from roughness to smoothness with cracks. The UV-visible spectroscopy reveals the red shift from 190 nm to 220 nm in the ultra violet region is attributed to π → π* transition. The direct and indirect optical band gaps were determined and found decrease from 4.99 eV to 4.62 eV with increased PVP wt % to 50:50. The dielectric constant observed decreases with increasing the frequency

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