Poly (p-phenylene vinylene) (PPV) was synthesized from p-xylylene bis(tetrahydrothiophenium chloride) using the Wessling route and characterized by Fourier Transform Infra-Red (FTIR) and UV-visible (UV-VIS) spectroscopic techniques. The significance of thermal treatment along with evolution of precursor polymer to polymer PPV was also studied through these spectroscopic techniques. Thermally Stimulated Current (TSC) measurements indicated the presence of crystallization, sulphonium group which occurred through the evolution from precursor polymer to polymer PPV during thermal treatment.