<jats:title>Abstract</jats:title><jats:p>Treatment of the metal reagent IrCl<jats:sub>3</jats:sub><jats:bold>⋅</jats:bold><jats:italic>n</jats:italic>H<jats:sub>2</jats:sub>O with two equivalents of 2‐pyridyl pyrazole (N^N)H (3‐<jats:italic>tert</jats:italic>‐butyl‐5‐(2‐pyridyl) pyrazole, (bppz)H and 3‐trifluoromethyl‐5‐(2‐pyridyl) pyrazole, (fppz)H), afforded the isomeric Ir<jats:sup>III</jats:sup> metal complexes with a general formula <jats:italic>cis</jats:italic>‐[Ir(bppz)<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>]H (<jats:bold>2 a</jats:bold>), <jats:italic>trans</jats:italic>‐[Ir(bppz)<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>]H (<jats:bold>3 a</jats:bold>), <jats:italic>cis</jats:italic>‐[Ir(fppz)<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>]H (<jats:bold>2 b</jats:bold>), and <jats:italic>trans</jats:italic>‐[Ir(fppz)<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>]H (<jats:bold>3 b</jats:bold>). Single‐crystal X‐ray diffraction studies on <jats:bold>2 b</jats:bold> and <jats:bold>3 a</jats:bold> revealed the coexistence of two pyrazolate chelates and two terminal chloride ligands on the coordination sphere. Subsequent reactivity studies confirmed their intermediacy to the preparation of homoleptic <jats:italic>mer</jats:italic>‐[Ir(bppz)<jats:sub>3</jats:sub>] (<jats:bold>1 a</jats:bold>) and <jats:italic>mer</jats:italic>‐[Ir(fppz)<jats:sub>3</jats:sub>] (<jats:bold>1 b</jats:bold>) that showed dual intraligand and ligand‐to‐ligand charge‐transfer phosphorescence at room temperature. To attain bright, room‐temperature phosphorescence further, we then synthesized two isoquinolinyl pyrazolate complexes, <jats:italic>mer</jats:italic>‐[Ir(bipz)<jats:sub>3</jats:sub>] (<jats:bold>4 a</jats:bold>) and <jats:italic>mer</jats:italic>‐[Ir(fipz)<jats:sub>3</jats:sub>] (<jats:bold>4 b</jats:bold>) ((bipz)H=3‐<jats:italic>tert</jats:italic>‐butyl‐5‐(1‐isoquinolyl) pyrazole and (fipz)H=3‐trifluoromethyl‐5‐(1‐isoquinolyl) pyrazole). Their orange luminescence is mainly attributed to the mixed MLCT/ππ* transition, and the quantum yields were as high as 86 (<jats:bold>4 a</jats:bold>) and 50 % (<jats:bold>4 b</jats:bold>) in degassed CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub> solution at RT. The organic light‐emitting diodes (OLEDs) were then fabricated by using <jats:bold>4 a</jats:bold> as a dopant, giving orange luminescence with CIE<jats:sub><jats:italic>x</jats:italic>,<jats:italic>y</jats:italic></jats:sub>=0.55, 0.45 (CIE<jats:sub><jats:italic>x</jats:italic>,<jats:italic>y</jats:italic></jats:sub>=the 1931 Commission Internationale de L’Eclairage (<jats:italic>x</jats:italic>,<jats:italic>y</jats:italic>) coordinates) and peak efficiencies of 14.6 % photon/electron, 34.8 cd A<jats:sup>−1</jats:sup>, 26.1 lm W<jats:sup>−1</jats:sup>. The device data were then compared with the previously reported heteroleptic complex [Ir(dfpz)<jats:sub>2</jats:sub>(bipz)] (<jats:bold>5</jats:bold>) ((dfpz)H=1‐(2,4‐difluorophenyl) pyrazole), revealing the possible effect of the bipz chelate and phosphor design on the overall electrophosphorescent performance, which can be understood by the differences in the carrier‐transport properties.</jats:p>