The first example of an unusual 21,23-dithiaphlorin containing pyrrole and aryl groups at the sp³ meso carbon that is present between the pyrrole and thiophene rings was isolated from the condensation of 2,5-bis(arylhydroxymethyl) and pyrrole under mild acid catalyzed conditions. The crystal structure revealed that the macrocycle is significantly distorted because of the presence of the sp³ meso carbon.