Herein, we demonstrate that oxidative inner-bond cleavage represents an effective strategy for the synthesis of figure-eight π-systems (Fig. ). The development of internal-modification strategies is an emerging research area in organic synthesis; representative examples of such strategies are molecular surgery and skeletal editing . We herein report that the catalytic oxidative cleavage of an internal double bond of the commercially available polycyclic aromatic hydrocarbon (PAH) dibenzo[g,p]chrysene (DBC; 1a, R = H), affords the figure-eight electron-accepting aromatic macrocycle cyclobisbiphenylenecarbonyl (CBBC; 2a, R = H) with high scalability (up to 3.3 g) and excellent enantioselectivity (94% ee). The construction of the central ten-membered ring of CBBC via a conventional bottom-up approach would be extremely difficult, as the intramolecular reductive homo-coupling of 2,2′dihalobenzophenone tends to occur instead of the desired intermolecular dimerization . Although 2a was first reported in 1934, its synthesis required a stoichiometric amount of toxic sodium dichromate in refluxing acetic acid ; considering the requirement for such harsh and toxic conditions, it is hardly surprising that only two CBBC derivatives have been reported over the last ninety years . Thus, detailed systematic investigations into the fundamental physical properties and functionalization of 2a remain elusive to date.