A convenient method was developed for the synthesis of 4-arylstyrenes containing residues of polycyclic aromatics or triphenylamine. The method is based on the microwaveassisted Suzuki-Miyaura cross-coupling reaction. The optical properties of the compounds were studied. High fluorescence quantum yields of 4-arylstyrenes make them promising monomers for the synthesis of polymers that can find use as photovoltaic and sensor materials.