The intramolecular double cyclization of bis(3-bromo-2-thienyl)acetylenes though a lithium-halogen exchange reaction with tBuLi followed by treatment with elemental sulfur produces two thiophene-fused thieno[3,2-c](1,2-dithiin)s. The subsequent dechalcogenation from the 1,2-dithiins with copper nanopowder affords tetrathienoacenes. On the basis of this two-step procedure, a series of trialkylsilyl-terminated, fused oligothiophenes, including hexathienoacene (a six thiophene-fused system) and octathienoacene (an eight thiophene-fused system), were synthesized. In the UV/Vis absorption and fluorescence spectra of the fused oligothiophenes, the absorption and emission maxima shift to longer wavelengths, as the pi-conjugation length increases. Their maximum wavenumbers have linear relationships with the reciprocal number of thiophene rings consisting of the pi-conjugated frameworks. In the cyclic voltammograms, all the compounds show reversible oxidation waves, the first oxidation potential of which shifts to less positive as the conjugation length increases. Among them, the octathienoacene also shows a reversible second oxidation process. Indeed, its chemical oxidation with an excess amount of NO(+)SbF(6) (-) produces the dication as a golden crystal. The crystal structures of the neutral octathienoacene and its dication were determined by X-ray crystallography. While in the neutral state, the octathienoacene has a benzenoid structure with a large bond alternation of about 0.04 A, its dication has a quinoid structure in which two cationic charges are mainly localized on the terminal rings.