Four new cationic iridium (III) complexes: [(cf3piq)2Ir(pzpy)]+PF6− (Ir1), [(cf3piq)2Ir(pzpyz)]+PF6− (Ir2), [(cf3piq)2Ir(impy)]+PF6− (Ir3), and [(cf3piq)2Ir(impyz)]+PF6− (Ir4) (where cf3piq=1‐(4‐(trifluoromethyl)phenyl)isoquinoline, pzpy=2‐(1H‐pyrazol‐3‐yl)pyridine, pzpyz=2‐(1H‐pyrazol‐3‐yl)pyrazine, impy=2‐(1H‐imidazol‐2‐yl)pyridine, and impyz=2‐(1H‐imidazol‐2‐yl)pyrazine) have been synthesized and fully characterized. The single crystal structure of Ir3 has been determined by X‐ray diffraction, and confirmed to have two hydrogen bonds (C14−H14⋅⋅⋅N2 and C57−H57⋅⋅⋅N9) and one intermolecular π‐π stacking interaction. The UV‐vis absorption, photoluminescence, and electrochemistry properties of all complexes have been studied. These complexes emit orange‐red photoluminescence with quantum yields of 28–46 % and excited state lifetimes of 0.48‐0.65 μs in CH2Cl2 solution at room temperature. Based on the DFT calculations, we concluded that their emission originated predominantly from a hybrid 3MLCT/3ILCT excited state.