(E)-1,2-bis(2-thienyl)vinylene (TV), (E)-1,2-bis(3-octyl-2-thienyl)vinylene (TOV), (E)-1,2-bis(3-(2-ethylhexyl)-2-thienyl)vinylene (T2EHV), and (E)-1,2-bis-[2,2’-bithienyl] vinylene (BTV) have been synthesized by a combination of formylation reaction and Mc Murry dimerization. UV–Vis spectra of BTV showed the longest wavelength absorption, TOV and T2EHV showed a bathochromic shift to the red compared with TV, due to an increment of delocalization of the conjugated π-system as the result of the weakening of the carbon–carbon double bonds of the thienyl rings due to the substitution of one hydrogen by the alkyl group. Based on optical data, the effect of linear and branched alkyl chain and extension of conjugation length on the electronic properties is discussed. ¹H, ¹³C-NMR, UV–Visible, Fluorescence data are discussed and theoretical DFT and TD-DFT calculations of ground state and excited states have been also considered in the analysis and explanation of results.