Motivated by the chiral supramolecular structures of chlorophylls in photosynthesis proteins, i. e., special pairs present in purple photosynthetic bacteria, photosystems‐I, and ‐II, a chiral porphyrin dimer was designed, synthesized, and resolved to give optically pure forms. Synthesis of the dimer was achieved by using 5,10‐diarylporphyrin as the starting material. The stereochemistry of the dimer was speculated by comparing experimentally and theoretically obtained circular dichroism spectra. Clear circularly polarized luminescence spectra were obtained at 636 nm with dimensionless Kuhn's anisotropy value of ∼2.0 × 10−3.