The coordinatively unsaturated bis-chelated iridium(III) complex, [Ir(2-Bubzq)2Cl] (2-BubzqH = 2-butyl-benzo[h]quinoline), denoted as complex 1, was obtained by reacting iridium(III) trichloride with 2-BubzqH in a 1 : 2 molar ratio. The results were in contrast to the common view that a chlorine-bridged dimer, [Ir(L)2Cl]2 (L = bis-chelate ligand), is formed under the corresponding conditions. A single-crystal X-ray diffraction structural analysis revealed that complex 1 has a five-coordinate geometry with a distorted square pyramidal configuration. The optical resolution of complex 1 was measured chromatographically on a chiral column, yielding Δ and Λ as enantiomers. The resolved enantiomers were stable enough against racemization in CDCl3 as confirmed by the vibrational circular dichroism measurements. Complex 1 reacted with carbon monoxide (CO) to give [Ir(2-Bubzq)2(CO)Cl] and with 1,10-phenanthroline (phen) to give [Ir(2-Bubzq)2(phen)]Cl within a minute with its absolute configuration (ΔΛ chirality) maintained.