Two oligoparaphenylene‐derived macrocycles were prepared using the anthracene photodimerization−cycloreversion strategy. The computational and experimental properties of these cyclic oligoparaphenylenes were conducted and compared with that of [12]cycloparaphenylene. We report the efficient syntheses of two novel oligoparaphenylene‐derived macrocycles using the anthracene photodimerization−cycloreversion strategy. Their photophysical, electrochemical, and computational properties, in comparison with that of [12]cycloparaphenylene, show intriguing effects of π‐conjugation interruption and anthracene incorporation. [ABSTRACT FROM AUTHOR]