Four phenylenevinylene oligomers (1-4) have been synthesized and characterized by cyclic voltammetry, absorption spectroscopy and photoluminescence (PL). Two of the oligomers contain a tri-substituted central benzene ring, while one contains a tetra-substituted central ring. These oligomers were prepared in an effort to increase hole and electron mobility in organic materials via extension of conjugation to two dimensions. Optical and electrochemical evidence is given for significant interactions of the alkoxy-substituted styryl units of 3 that are attached to the central benzene ring in meta positions. The tetra-substituted oligomer (4) also exhibits strong interactions between the pair of para substituted arms. The photoluminescence (PL) quantum yield for the tetra-substituted oligomer is high, indicating that it is an excellent candidate for the active layer in organic light-emitting diodes.