An efficient method for the synthesis of PPV based polymers, poly (2,5-dimethyl-1,4-phenylene vinylene) (DMe-PPV) and poly (2,5-dimethoxy-1,4-phenylene vinylene) (DOMe-PPV) were developed using 2,5-dimethyl-1,4-bis (chloromethyl) benzene and 2,5-dimethoxy 1,4-bis (chloromethyl) benzene via vapor phase pyrolysis and followed by vapor deposition polymerization. The structure of polymer films were confirmed by FT-IR, solid state NMR and elemental analysis. Thermal gravimetry analysis reveals that the precursor polymer films form a conjugated polymer after thermal conversion at 250°C. The optical and electrical properties of the polymer films were investigated by UV-Vis absorption and photoluminescence spectroscopies. Electroluminescent devices were fabricated using these polymers.