Treatment of [Ir(PPh3)(3)Cl] with 2-[5-(pyridin-2-yl)-1H-pyrrol-2-yl]pyridine (Hdpp) in refluxing toluene affords an unexpected pyrrole-metalated iridium(III) hydride complex, [Ir(K-C,N(2)-dpp)(H)(Cl)(PPh3)(2)] (1), via C-pyrrole-H activation, while the presence of the base (KOBu)-Bu-t as the deprotonation reagent produces a pyridine-metalated iridium(III) hydride complex, [Ir(K-C,N,N(3)-dpp)(H)(PPh3)(2)] (2), via C-pyridine-H activation. Treatment of [Ir(PPh3)(3)Cl] prepared by a convenient method with Hdpp in the presence of (KOBu)-Bu-t under the refluxing mixture solvent toluene/methanol (2:1, v/v) generates the N,N-chelating complex [Ir(K-N,N(2)-dpp)(H)(Cl)(PPh3)(2)] (3) together with 1 and the N,N-chelating dihydride complex [Ir(K-N,N(2)-dpp)(H)(2)(PPh3)(2)] (4). Complex 4 is also readily produced by the reaction of [Ir(PPh3)(3)Cl] and Hdpp in the presence of KOtBu under refluxing methanol or by the reaction of IrCl3 and PPh3 in refluxing 2-ethoxyethanol. Complexes 1-4 are fully characterized by NMR, IR, and UV-vis spectroscopy and X-ray diffraction analysis. The dpp(-)/dpp(2-) ligand shows rich coordination capability, of which pyridine- and pyrrole-cyclometalated coordination modes are first reported. The formation of structural isomers 1 and 3 involved the selective activation of the C-H and N-H bonds of Hdpp is rationalized by theoretical calculations.