The influence of reaction conditions and monomer selection on the resulting film composition and luminescence properties of poly(p-phenylene vinylene) (PPV) prepared by chemical vapor deposition is investigated. Greater aliphatic hydrocarbon incorporation into the polymer is observed when ol,dibromo-p-xylene is used as the starting monomer, as compared to alpha,alpha＇-dichloro-p-xylene. This difference has implications for the peak photoluminescence output of the resulting PPV films, with the Br-PPV shifted to higher energies compared to CI-PPV. From X-ray photoelectron spectroscopy, temperature dependent infrared spectroscopy, and Raman spectroscopy, the reaction pathway for aliphatic hydrocarbon incorporation into the polymer chain is deter mined to be fragmentation of the monomer during the pyrolysis step.