As a new type of pi-conjugated macrocycles, 1,8-anthrylene-butadiynylene cyclic tetramers were synthesized by metal-catalyzed oxidative coupling reactions. The fluorescence spectrum of the nonsubstituted derivative indicated partial formation of an excimer in the excited state. The macrocyclic structure undergoes rapid interconversion between two enantiomeric diamond prism structures. These spectroscopic and structural features are compared with those of ethynylene analogues.