The salt (η5-pentamethylcyclopentadienyl){bis(pentafluorophenyl)thiomethylphenylphosphine-κ2 S,P)chloroiridium(III) tetrafluoroborate, [(η5-C5Me5)IrCl{κ2 S,P-(C6F5)2PC6H4SMe-2}]BF4, crystallizes as a conglomerate in the orthorhombic crystal system in space group P212121 with unit cell parameters a = 9.9621(9) A, b = 16.7793(15) A, c = 18.5040(16) A, V = 3093.1(5) A3, Z = 4, d calc = 2.014 g·cm−3. The structure of the S Ir, S S stereoisomer reveals three-legged piano stool geometry about Ir, with Cp*-Ir, Ir-P, Ir-S and Ir-Cl distances of 1.847(5) A, 2.2791(14) A, 2.3451(13) A, and 2.3840(12) A respectively.