A cyclophane-type of dimeric quinquethiophenes (4a-e) with the bridge chains consecutively varying from two to six methylenes has been synthesized and studied as ideal π-dimer models. The double-decker structures of these compounds are verified by upfield shifts for the proton NMR signals of the inside thiophenes, as compared to those of monomeric dimethylquinquethiophene (3). The electronic absorption and emission spectra of 4a-e are perturbed by through-space π-electronic interactions involving exciton-exciton coupling between the two overlapped quinquethiophenes, which become marked with shortening of the bridged alkylene chains. One-electron oxidation of 4a-e with FeCb in dichloromethane results in the appearance of specific polaronic bands in the near-infrared region of the electronic absorption spectra, due to the generation of a radical cation species (polaron) on one of the quinquethiophenes, which electronically interacts with the remaining neutral species. Two-electron oxidation of 4a-e introduces spectral changes, revealing that the resulting two quinquethiophene radical cations readily form an intramolecular π-dimer, thanks to their close stacking, in contrast to the difficult formation of an intermolecular π-dimer from 3. The π-dimeric spectra of 4b-e are comprised of two strong absorption bands, similar to that of 3, the low-energy band of which is considerably red-shifted by an effective π-dimeric interaction depending on the lengths of the bridged alkylene chains. Quite different is the spectrum of 4a with three absorption bands inherent in π-dimer, presumably because the two short bridging chains of 4a force the π-dimer to take a constrained, strongly interactive structure.