A spectroscopic and computational study of a series of 2,5-bis(2-thien-2-ylethenyl) thiophene-based oligomers with a para-R-arylethenyl substituent is reported. The primary aim of this investigation is to increase understanding of how charge moves through these molecules by comparing the neutral and oxidized structures for each molecule. To this end, the B3LYP/6-31G(d) computational method was used to calculate the geometry and vibrational spectra for all molecules considered and their oxidation products. For vibrational data, mean absolute deviations for frequencies between experimental and theoretical results ranging from 2 to 18 cm(-1) were obtained. Experimental Raman spectroscopy, in conjunction with calculated bond length analyses, was used to gain an insight into the position and delocalization of the charged defect on the oxidized oligomers. The relative frequencies of different ethylene stretching modes served as a particularly useful probe in this regard. It was found that the ethenyl spacers do not impede pi-electron delocalization and, therefore, give rise to a longer conjugation length relative to the corresponding terthiophenes. Furthermore, the para-R-arylethenyl substituent was found to orientate the charged defect toward a specific region of the 2,5-bis(2-thien-2-ylethenyl)thiophene conjugation path.