The systematic synthesis of poly(phenylvinylene) (PPV) derivatives by the Wittig-Homer reaction is reported. The phenyl units of the PPV structure are methodically substituted by naphthyl and anthryl units to form a homologous series of structures. The 2,6 attachment of the vinylene linkage on the anthryl ring provides novel structures that have not been reported before due to their synthetic inaccessibility. The introduction of naphthyl units results in a hypsochromatic shift in the absorption and em ission spectra, while the introduction of anthryl units leads to a bathochromatic shift relative to the naphthalene structures. The observed structural variation of the spectroscopic properties is explained in terms of a combination of the increased conjugation of the substituent acene units and the decreased electronic contribution across the vinyl linkage.