(Alkoxycarbonyl)iridium compounds of type [Irl2(CO2R)(CO)L2] have been prepared by the reaction of K[Ir(CO)2l4] with nitrogen bases L and alcohols ROH. The reaction takes place through nucleophilic attack of the alcohols on the intermediate cations [lrl2(CO)2L2]+, some of which have been isolated. Other (alkoxycarbonyl)iridium compounds containing triphenylphosphine (Y), [Irl2(CO2R)(CO)Y2] and [Irl(CO2R)(CO)2Y]2 were obtained by the reaction of [Irl(CO)2(Y2)] and [lr(CO)3Y]2 respectively with iodine and alcohols.