2,5-Bis[(3,4-ethylenedioxy)thien-2-yl] thiophene monomers bearing 3′-hydroxymethylene (2), 3′-hydroxyethylene (3), 3′-acetoxyethyl (4) and 3′-acetoxyl (5) functions were prepared in a short bidirectional synthesis using Kumada–Corriu or Stille chemistry. The newly prepared monomers are stable enough in organic solvents at RT in the absence of acids and can be safely stored without exclusion of oxygen, at 4°C in the dark. The chloroform solutions of 2–5 exhibit a blue-shifted λmax in the range of 345–352nm, when compared to 2,5-bis[(3,4-ethylenedioxy)thien-2-yl] thiophene (1). Smaller shifts were observed in the fluorescence spectra where all λmax values were centered in the range of 438–440nm, similar to the parent unsubstituted 1 (439nm) with fluorescence quantum yields φf=2.2–2.8%, that was roughly half of the monomer 1 reference value (4.8%). Cyclic voltammetry was employed to investigate the electrochemical behaviour of the monomers. Polymer films deposited by repeated potential cycling show oxidation potentials ranging from 320 to 540mV. AFM analysis shows that these polymers display large active surface because of their roughness. All the polymers exhibit a broad absorption spectrum with a λmax ranging from 464nm to 533nm.