Functional 2-pyrazolyl-6-phenylpyridine chelates-namely, (pzpyph(Bu))H-2 and (pzpyph(CF3))H-2 and phosphines-are successfully employed in the preparation of emissive Ir(III) metal complexes, for which the reaction with phosphine such as PPh3, PPh2Me, and PPh2(CH2Ph) afford corresponding Ir(III) complexes [Ir(pzpyph(Bu))(PPh3)(2)H] (1a), [Ir(pzpyph(CF3))(PPh2R)(2)H] (2a-2c), R = Ph, Me, CH2Ph, which also show an equatorial coordinated hydride. In contrast, treatment with 1,2-bis(diphenylphosphino)benzene (dppb) and 1,2-bis(diphenylphosphino)ethane (dppe) yields the isomeric products [Ir(pzpyph(Bu))(dppb)H] (3a) and [Ir(pzpyph(Bu))(dppe)H] (3b), for which the distinctive, axial hydride undergoes rapid chlorination, forming chlorinated complexes [Ir(pzpyph(Bu))(dppb)Cl] (4a) and [Ir(pzpyph(Bu))(dppe)Cl] (4b), respectively. On the other hand, upon extensive heating of 2c, one of its coordinated PPh2(CH2Ph) exhibits benzyl cyclometalation and hydride elimination to afford [Ir(pzpyph(CF3))(PPh2R)(PPh2R')] (5c and 6c) R = CH2Ph and R' = CH2(o-C6H4) as the kinetic and thermodynamic products, respectively. Their structural, photophysical, and electrochemical properties are examined and further affirmed by the computational approaches.