The reaction of (4-methyl-pyridine-2-iloxy)dimethylsilane (NSi Me-H, 1) with [RhCl(coe)2]2 gives the rhodium(III) complex [Rh(Cl)(κ 2-NSi Me)] (2), which reacts with a stoichiometric amount of AgCF3CO2 to afford [Rh(κ 2-CF3CO2)(κ 2-NSi Me)2] (3). Complexes 2 and 3 have been fully characterized by elemental analysis and NMR spectroscopy. The solid-state structure of 3 has been confirmed by X-ray diffraction analysis. Moreover, the activity of complex 3 as catalyst for the reaction of secondary amines with CO2 (3 bar) and hydrosilanes has been studied. The outcomes of these catalytic studies show that under these conditions complex 3 promotes the selective formation of silylcarbamates.