A novel tandem single-electron oxidative ring expansion reaction has been developed for the construction of the saddle-shaped polycyclic arenes fused with cyclooctatetraene, that is, dibenzo[3,4:7,8]cycloocta[1,2-l]phenanthrenes (dbCOTPs). The combination of Cu(OTf)2 catalyst with DDQ triggered the selective oxidation of o-biphenyl-tethered methylenecirculenes fused with a seven-membered ring, giving rise to the formation of the corresponding eight-membered ring fused dbCOTPs. The present tandem ring expansion of a seven- to an eight-membered ring takes place via the selective single-electron oxidation of the benzylidene moiety, intramolecular spirocyclization, and 1,2-aryl migration sequence.