Novel 1,3-dithiole[4]dendralene derivatives 3 with two thiophene spacers were synthesized. Cyclic voltammetry and spectroelectrochemistry suggested the dications of most derivatives of 3 have dimeric thiophene quinoid radical cation structures, while tetramethyltetrakis(methoxycarbonyl) derivative 3Bd adopts a vinylogous TTF dication structure.