A new series of cyclometalated iridium(III) complexes with isocyanoborate ligands [Ir(R2ppy)2(L)(CNBR'3)] (R = H or F; L = CNC6H4Cl-4 or PPh3; R' = Ph, C6F5 or C6H4Cl-4), [Ir(biqb)(ppy)(CNBR''3)] (R'' = C6F5 or C6H4Cl-4) and {Ir(ppy)2(CN)n[CNB(C6F5)3]2-n}(-) (n = 0 or 1) have been synthesized and characterized. Three of these complexes have also been structurally characterized by X-ray crystallography. The photophysical and electrochemical properties of these complexes have been investigated. The effects of isocyanoborate ligands on the luminescence properties of these iridium(III) complexes are also described.