The synthesis of a series of crown ether substituted vinylogous tetrathiafulvalenes (TTFVs) has been carried out through oxidative coupling of bisdithiafulvenes. These new receptors have been fully characterized using electrochemical, spectroelectrochemical, and molecular modeling experiments. These studies show that, upon oxidation, either a clip movement (TTFVs 3a,b) or a stretch movement (TTFV 3c) occurs, depending on the length of the crown ether chains. Preliminary electrochemical studies, undertaken on TTFV 3c in dichloromethane, show a little shift of the first standard oxidation potential toward more positive values upon addition of the Pb(2+) ion, but a considerable variation of the electron-transfer kinetics. This result introduces an interesting concept for the preparation of sensors not based on thermodynamic variations but on kinetic modifications of the electron transfer.