A synthesis route to soluble high molecular weight poly(p-xylylene) derivatives has been investigated. This method provides a versatile route to poly(phenylenevinylene) (PPV) from a precursor polymer that is amenable to the conventional nonaqueous processing techniques. To investigate the mechanism in the solvent mixture, monomethylformamide (MMF)/CH2Cl2 (60/40), the influence of the leaving group and polarizer oi. the monomer was studied. The evaluation of the molecular weight of the polymer, the polymer yield, and the residual low molecular weight fr action indicates that only the kind of polarizer has an effect on the reaction in contrast with the leaving group, having no observable effect.