In the present work, Polyvinyl pyrrolidone/polyphenylene oxide (PVP/PPO) membranes have been synthesized by using spin coating technique. Optical and luminescence properties of membranes were studied by using optical absorption and florescence spectroscopic techniques. Two excitonic bands under the absorption edge have been observed in these samples. The optical absorption edge has been observed to shift towards higher wavelength side upon addition of PPO in the PVP matrix. A photoluminescence spectra in visible region (at ~500 nm) was observed to be enhanced in immiscible blend (50/50) composition with that for PVP polymer. Improved luminescence in visible region indicates the modification in structure-property relationship in PVP/PPO blend, which is required for its application in designing optical devices.