A new type of molecular wire la-c with tetrathiafulvalene (TTF) units was synthesized and characterized. The UV-vis spectra and electrochemistry results showed that comparing with PPE, these polymers had smaller HOMO-LUMO band gap, and the HOMO level of polymer 1a (-5.05 eV) was closer to the work function energy of Au electrode. Thermal stability analyses indicated that these polymers had good thermal stability. All of the results showed that the introduction of TTF units made polymers la-c better candidates for molecular wires than PPE. (c) 2006 Wiley Periodicals, Inc.