Here we report the synthesis and physical characterization of four substituted phenylenevinylene molecules, 1-4, which serve as short chain model oligomers of poly(1,4-phenylenevinylene). Quantum mechanical calculations on alkoxy substituted stilbene derivatives 1 and 2 reveal a direct correlation between the torsional angles and the substituent pattern. HOMO and LUMO energy levels were calculated for all four compounds and showed that the introduction of alkoxy substituents reduce the energy gaps between the ground and first excited singlet states of these molecules. In addition, absorption spectra, fluorescence life-times and quantum yield data of the four compounds are presented.