Abstract Six triple-layered [2.2]metaparacyclophanes have been prepared using general synthetic methods such as the Stevens rearrangement-Raney nickel desulfurization method, pyrolysis of bissulfone, and photo-induced desulfurization. The pyrolysis of bissulfone has turned out to be the most useful and convenient method for preparation of the intermediate double-layered [2.2]metaparacyclophanes because of simple experimental process and excellent yields. The unexpected formation of compound 9 during the photo-induced desulfurization of 7 was explained by a unique skeletal rearrangement of the intermediate 8 on irradiation.