Microwave radiation (MWR) was used to induce the elimination reaction of the poly(phenylene vinylene)-polyelectrolyte precursor polymer (PPV precursor) into the fully conjugated polymer. The process was applied mainly to the unsubstituted PPV and was followed by infrared spectroscopy. The extent of the elimination process was also determined from the amount of residual sulfur in the film after the irradiation process. The microwave-induced elimination process was also attempted using PPV precursor films that had been impregnated with anionic compounds containing iron. The molecular mechanisms for the observations are discussed and comparison with the elimination reaction induced by other energy sources is also made.