The thienoviologen series 4,4′-(2,2′-bithiophene-5,5′-diyl)bis(1-alkylpridinium)X₂, mVX₂ with X = counterion is a new class of electron acceptor materials which show very interesting electrochromic and electrofluorescence properties. Depending on the length, m, of the promesogenic alkyl chains, and on the counterion, thienoviologens might become liquid crystals. Here, we present the mesomorphic behaviour, and the electrochemical and spectroelectrochemical properties in solution of new thienoviologens of the series mVI₂ and mV(NTf₂)₂ (I = iodide; NTf₂⁻ = bis(tri-fuoromethylsulfonyl)imide) with m = 8, 12. Interestingly, we found that only the compounds 12VX₂ are liquid crystals, exhibiting a calamitic behaviour in contrast to the homologous compounds of the series with m = 9–11 and X = NTf₂⁻, which showed columnar rectangular mesophases. The electrochemical study here reported allowed us to explain for the first time the anomalous behaviour of these thienoviologens already observed in cyclic voltammetry, where two apparently irreversible redox processes occur. This can be explained by a comproportionation reaction in which the neutral species rapidly reduces the dication to the radical-cation, due to its strong reducing power. Electrochemical reduction of the thienoviologens causes electrochromism since a new absorption band, occurring at 660 nm in the electronic spectra, appears with the negative potential bias applied. With a LUMO level of 3.64 eV, similar to those of the C₆₀ and of other n-type materials, these compounds can find applications in several electronics devices, where their liquid crystalline properties can be used to control film morphology and geometry, provided they have good electron mobility.