Oxidative addition of aliphatic alcohols to (C(8)H(14))IrCl(PMe(3))(3) in benzene yields the cis-hydrido-alkoxo products mer-cis-HIr(OR)Cl(PMe(3))(3) (R = Me, Et, 1-pentyl, 2-propyl). The analogous hydroxo complex is prepared by oxidative addition of water in THF. The addition rate depends on the nature of the alcohol (methanol > 1-pentanol >> 2-propanol and methanol > water). The reaction is retarded in polar media but accelerated by protic cosolvents. Anionic ligand redistribution involving chloride and alkoxide (or hydroxide) competes with the oxidative addition reaction. A detailed kinetic study suggests that the 16-electron IrCl(PMe(3))(3) is the species undergoing the oxidative addition, and mer-cis-HIr(OR)Cl(PMe(3))(3) is the kinetic product. The reaction proceeds by a single-step nucleophilic attack of the metal on the O-H proton. Pi-donation by chloride stabilizes the transition state and governs the stereochemical course of the reaction. Protic solvent aggregation in the transition state in an apolar medium is suggested. mer-cis-HIr(OH)Cl(PEt(3))(3), obtained by water addition to IrCl(PEt(3))(3), was crystallographically characterized, showing an unusual hydrophobic cage around the hydride ligand.