The synthesis and structures of a series of cyclometalated iridium(III) complexes based on benzoxazole derivatives and triphenylphospine are reported. These complexes have a general formula (C^N)(2)Ir(Cl)(pph(3)) [where C^N is a monoanionic cyclometalating ligand, dfpbo = (difluorophenyl)benzoxazolato, pbo = 2-phenylbenzoxazolato, nbo = 2-(2-naphthyl)benzoxazolato, and pph(3) is a triphenylphospine ligand]. The complexes (dfpbo)(2)Ir(Cl)(pph(3)) (2a), (pbo)(2)Ir(Cl)(pph(3)) (2b), and (nbo)(2)Ir (Cl)(pph(3)) (2c) have been structurally characterized by X-ray crystallography. Complex 2a shows facile umpolung in the phenyl rings of the arylphosphine ligand and displays a catalytic propensity for water splitting.