A study of reactions of dimeric siloxide iridium complex, [{(cod)Ir(μ-OSiMe₃)}₂] (1) with vinyltriethoxysilane and vinyltrimethoxysilane has revealed a new type of the reaction—alkoxy group transfer from silicon to iridium with a simultaneous transfer of a siloxy group from iridium to silicon—as a result of which vinyldialkoxytrimethyldisiloxane and dimeric alkoxide iridium complex [{(cod)Ir(μ-OR)}₂] (3) are formed. The structure of [{(cod)Ir(μ-OEt)}₂] (3a) has been solved by X-ray diffraction.