The main obstacle to a widespread application of porphycenes, the first structural isomer of porphyrins, lies in the lack of an efficient and economical method of their production. This study reports a series of unsymmetrical porphycenes prepared by acid‐catalyzed oxidative coupling of AA‐ and BB‐dipyrroethenes, or AB‐type dipyrroethenes. The type and position of substituents in the unsymmetric porphycenes enabled fine‐tuning of the optical and electronic properties. The graphic shows an example of crystal structure of AABB‐porphycene that contains 3,5‐bis(trifluoromethyl)benzene at 9,10‐position and benzene at 19,20‐position of the porphycene framework. More information can be found in the Full Paper by N. Xu, T. Ono, and Y. Hisaeda on page 11680.