Results on CO2 hydrogenation to formic acid in the presence of RhCl(PPh3)(3) and HRh(PPh3)(4) complexes at room temperature and a pressure of 6.0 MPa (CO2 : H-2 = 2) are presented. Certain features of the reaction in the presence of these complexes are compared. On the basis of kinetic data and P-31 NMR measurements, it was shown that catalyst deactivation is mainly due to the elimination of PPh3. A method for stabilizing the catalyst by introducing inorganic salts into the reaction solution was proposed. The new effective catalyst system including, RhCl(PPh3)(3), PPh3, and KNO3 makes it possible to hydrogenate CO2 in 100% yield.