Five new acceptor-π–TTF-π-acceptor (A–D–A) triads that contain pyridine, quinoline, nitrophenyl or nitrofuryl groups as acceptor unit have been synthesized by two-fold Wittig olefination reactions and their electrochemical behavior has been studied by cyclic voltammetry (CV). The intramolecular charge transfer (ICT) band in these molecules was characterized by UV–visible electronic absorption spectroscopy and these studies were completed by DFT calculations in the gas phase. These materials appear to be good candidates for the preparation of electroactive discrete metal complexes or coordination polymers as well as for the preparation of radical cations salts.