Poly[(2-(2-phenylethenyl)-1,4-phenylene)vinylene] (PPEPV), poly[(2-methoxy-5-(2-phenylethenyl)-1,4-phenylene)vinylene] (PMPEPV), and their copolymers containing 1,4-phenylenevinylene (PV) units [poly(PEPV-co-PV)s and poly(MPEPV-co-PV)s] were synthesized via water soluble, polyelectrolyte precursor polymers. Electronic spectral characteristics of the polymers clearly demonstrate that the crossconjugation between the main chain andthe pendant 2-phenylethenyl (β-styryl) unit is insignificant. Electrical conductivities of FeCl 3 -doped PPEPV and PMPEPV were on the order of 10 -4 S cm -1 , which were lower than those of copolymers containing PV units. This is ascribed to the charge-transfer interactions between the dopants and styryl units in the side branch