In this article, we investigate a series of alpha,omega-dicyano end-capped oligothiophenes NC(C4H2S)(n)CN ranging in length from the dimer to the hexamer (n = 2-6), in the neutral state as pure solids, by means of Fourier transform IR and Fourier transform Raman (FT-Raman) spectroscopies. The cyclic voltammetry analysis of the compounds in dichloromethane reveals that most of them show two oxidation and two reduction waves (i.e., a dual or amphoteric electrochemical behavior), associated with the injection of either positive or negative charges into the pi-conjugated system. The doped species are characterized by in situ vis-near-IR and FT-Raman spectrochemistries. Density functional theory calculations have been also performed, at the B3LYP/6-31G** level, to assess information about the molecular geometries and vibrational features of the neutral and doped species and about the topologies of the molecular orbitals involved in the main electronic transitions that appear for the neutral forms in the visible spectral region and for the doped species in the near-IR region.