Poly(2,5-pyrrolylenevinylene) (PPRV) was obtained from the monomer, 2,5-bis(methylenedimethylsulfoniumchloride) pyrrole, which was prepared from 2,5-dimethylpyrrole by the modified sulfonium polyelectrolyte precursor route. The polymerization conditions for the preparation of precursor polymers were examined. The highest yield was obtained when the precursor polymer,poly(alpha-methoxy-2,5-pyrrolylene [poly(alpha-MeO-PRY)], was synthesized at -40 degrees C with the monomer/base concentration ratios of 0.5/0.2. PPRV obtained by the thermal elimination of the precursor polymer at 220 degrees C exhibited highest electrical conductivity, being the order of 6.9 x 10(-7) Scm(-1).