Tuning of the electrical and optical properties of a series of polyphenylenevinylene (PPV) derivatives has been demonstrated using photoluminescence spectroscopy. The synthesis of the title compounds is described and the effect of substituting electron-donating and electron-withdrawing groups in them is correlated with the photoluminescence spectra and electrochemical data. The compounds are shown to be suitable models leading to an understanding of the behavior of conjugated polymers as active layers in light-emitting diodes.