The polymerizability of nitrogen-containing bissulfonium salts was analyzed. The poor homopolymerization results were attributed to sluggish quinodimethane formation. However, copolymerizations with the non-nitrogenated analogue sulfonium salt were successful. We report here the synthesis and characterization of a series of poly(1,4-phenylene vinylene)-co-(2,5-pyridylene vinylene)s. Elemental analysis, FTIR, UV-vis and fluorescence studies demonstrate that the pyridilene units can be incorporated by the water soluble precursor route in PPV-type polymers with free-standing film formation properties.