Rhodium(III) and iridium(III) bipyricorrole complexes have been unprecedentedly reported. Single-crystal X-ray diffraction studies unambiguously evinced the molecular structures of metal complexes in octahedral geometry. The monoanionic platform of bipyricorrole effectively stabilizes metal ions in their higher oxidation states. It is worth mentioning that the fluorescence quantum yield of the rhodium(III) complex is 3-fold higher than that of free-base bipyricorrole.