The preparation of a novel fullerene‐thiophene derivative by Diels‐Alder addition of terthiophene S,S‐dioxide was demonstrated. Extrusion of SO2 from the adduct is an effective process that yields a stable cyclohexadiene‐1,4‐bisthiophene–C60 adduct in good isolable yield. The product has been accurately characterized and opens the way to synthesize new C60 derivatives “via” Diels‐Alder methodology without the possibility of cycloreversion. Electrochemical and spectroscopic properties of this macromolecule were studied and supported by theoretical calculations to interpret its electronic structure. The first approach to the electropolymerization of this macromonomer produces donor‐acceptor molecular wires providing a new and versatile way to fullerene‐based double cable polymers.
