We report excellent correlations between the first negative threshold potentials (VTHS) for electric conduction, electrochemical potentials, and computed lowest unoccupied molecular orbital energies in a series of phenylene-ethynylene oligomers bearing a sulfur-based anchoring unit and different electroactive substituents on the central benzene ring. The theoretical and electrochemical results strongly suggest that the peaks observed in the i-V curves have a true molecular origin and are associated with distinct unoccupied molecular levels of the compounds that are strongly localized on the central ring (except for compound I). This localization might account for the existence of a long-lived radical-anion state that permits lateral electron hopping and leads to charge trapping and storage.