A benzene solution of Cp*Ir(CO) 2 was irradiated for 10 h at room temperature, and then the reaction solution was exposed to air overnight, affording two cis–trans isomeric diiridium(Ir–Ir) complexes [Cp*Ir(μ-CO)(Ph)] 2 (1 and 4), a mononuclear iridium complex Cp*Ir(CO)(Ph) 2 (2), a diiridium(Ir–Ir) complex Cp* 2 (CO) 2 Ir 2 (μ 2 -C 6 H 4 ) (3), a novel hexanuclear iridium complex [Cp* 2 (μ 2 -Ph)(μ 2 -H)Ir 2 ](μ 3 -CO 2 )[Ir 4 (CO) 11 ] (5), and trace biphenyl. The molecular structures of complexes 1–5 have been determined by single-crystal X-ray diffraction analysis. Moreover, we studied the reactivities and possible formation paths of some of these complexes.