The reaction of hydrated iridium chloride with formic acid in refluxing ethoxyethanol afforded by an efficient way the known iridium carbonyl chlorido complex cis-[IrCl2(CO)2]-. The latter species was isolated and characterized as its corresponding PPN salt (PPN+ = bis(triphenylphosphane)iminium cation). The molecular structure of PPN[IrCl2(CO)2] ( 1) was confirmed by X-ray diffraction.