As a model of bacterial photosynthetic light-harvesting antenna, a large number of porphyrin units were organized into barrel-shaped macrorings. Two imidazolylporphyrinatozinc(II) molecules were linked through either unsubstituted thiophenes or 3,4-dioctylthiophenes 1 a and 1 b, respectively. These structures were spontaneously organized by complementary coordination of the imidazolyl to zinc and produced a series of self-assembled fluorescent polygonal macrorings under high dilution conditions. The ring size increased compared with previous m-phenylene examples. The size distribution was also controlled by the presence of octyl substituents. A wide distribution of macrorings from 7- to >15-mer was obtained from 1 a, whereas macrorings ranging from 7- to 11-mer with a maximum population focused at the 8-mer were formed with 1 b. The size distribution was governed by competition between entropy-favored, smaller-ring formation and the enthalpy-favored, less-strained larger macroring. The UV/Vis spectra showed a gradual redshift for the larger rings reflecting an increase in the transition dipole interactions.