The reaction of the cyclometalated chloro-bridged iridium(III) dimers [(ppy)(2) Ir(mu-Cl)](2) (ppyH = 2-phenyl pyridine) and [(tpy)(2)Ir(mu-Cl)](2) (tpyH = 2-p-tolylpyridine) with 3,5-diphenylpyrazole (Ph(2)PzH) in the presence of sodium methoxide resulted in the formation of heterobridged dimers [(ppy)(2)Ir(mu-OH) (mu-Ph(2)Pz)Ir(ppy)(2)] (1) and [(tpy)(2)Ir(mu-OH)(mu-Ph(2)Pz)Ir(tpy)(2)] (2). Interestingly, the reaction of [(ppy)(2)Ir(mu-Cl)](2) with 3(5)-methyl-5(3)-phenylpyrazole (PhMePzH) afforded both a heterobridged dimer, [(ppy)(2)Ir(mu-OH)(mu-PhMePz)Ir(ppy)(2)] (3), and the monomer [(ppy)(2)Ir(PhMePz)Cl] (4). The compound [(ppy)(2)Ir(PhMePz)OH] (5) containing a terminal OH was obtained in a hydrolysis reaction involving 4, sodium methoxide, and PhMePzH. Complexes 1-5 were characterized by X-ray crystallography and electrospray ionization high-resolution mass spectrometry. All of the complexes are luminescent at room temperature in their dichloromethane solutions. The luminescence of the dinuclear complexes is characterized by a single structureless band centered at lambda(max) = 550 nm (1 and 3) and 546 nm (2). The emission spectra of the mononuclear complexes 4 and 5 display vibronic structures with their lambda(max) values at 497 nm (4) and 513 nm (5). In each case, the main emission bands are accompanied by shoulder bands at 526 (4) and 534 nm (5). The quantum yields, calculated with reference to [Ir(ppy)(2)(bpy)]PF6 (Phi(CH3CN) = 0.0622), range from 0.11 to 0.17 for the dinuclear complexes and 0.045 to 0.048 for the mononuclear complexes. The lifetimes of the emission are in the microsecond region, suggesting the phosphorescent nature of the emission. Density functional theory (DFT) and time-dependent DFT calculations were performed on complexes 1 and 4 in the ground state to gain insight into the structural, electronic, and photophysical properties. Electrochemical studies on complexes 1-3 showed the presence of two consecutive one-electron-oxidation processes, assigned as the stepwise oxidation of the two Ir-III centers, i.e., Ir-III-Ir-III/Ir-III-Ir-IV and Ir-III-Ir-IV/Ir-IV-Ir-IV couples, respectively. The monomers displayed single-oxidation peaks. No reduction process was observed within the solvent cathodic potential limit.