<jats:title>Abstract</jats:title><jats:p>We synthesized four Ir<jats:sup>III</jats:sup> terpyridine complexes with three Cl<jats:sup>–</jats:sup> anions by using microwave irradiation. By introducing three Cl<jats:sup>–</jats:sup> anions to the Ir<jats:sup>3+</jats:sup> cation, it can be expected that the absorption and emission properties of the complexes change from π–π* to metal‐to‐ligand charge transfer (MLCT). These complexes having intrinsic <jats:italic>C</jats:italic><jats:sub>2<jats:italic>v</jats:italic></jats:sub> symmetry are suitable for analyzing orbital interactions. This symmetry has four irreducible representations, a<jats:sub>1</jats:sub>, a<jats:sub>2</jats:sub>, b<jats:sub>1</jats:sub>, and b<jats:sub>2</jats:sub>, which results in no degenerate orbitals. Charge transfers (CTs) from three nitrogen lone‐pair orbitals to the 5d<jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/tex2gif-inf-6.gif" xlink:title="urn:x-wiley:14341948:media:EJIC200801139:tex2gif-inf-6" /> and 5d<jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/tex2gif-inf-7.gif" xlink:title="urn:x-wiley:14341948:media:EJIC200801139:tex2gif-inf-7" /> atomic orbitals give three Ir–N coordination bonds in the in‐plane molecular orbital (MO) overlap of a<jats:sub>1</jats:sub> symmetry. These CTs are described by the 60th and 66th MOs in the [IrCl<jats:sub>3</jats:sub>(terpy)] complex, (terpy = 2,2′:6′,2″‐terpyridine). The antibonding combination of the 5d<jats:italic><jats:sub>xz</jats:sub></jats:italic> and the lone‐pair orbital of Cl<jats:sup>–</jats:sup> gives rise to the high‐lying HOMO in b<jats:sub>1</jats:sub> symmetry. The back CT, the highest occupied molecular orbital (HOMO) (b<jats:sub>1</jats:sub>) → the lowest unoccupied molecular orbital (LUMO) (b<jats:sub>1</jats:sub>), corresponds to MLCT, and the small‐energy excitation is confirmed by the long wavelength <jats:italic>λ</jats:italic><jats:sub>max</jats:sub> ≈ 500 nm in the absorption spectroscopy.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</jats:p>