The thermodynamics involved in the catalytic hydrogenation of CO₂ have been examined extensively. By assuming that methanol and dimethyl ether (DME) are the main products, two reaction systems each consisting of two pararell reactions were analyzed and compared in terms of the equilibrium yield and selectivity of the useful products, methanol and DME. The calculation results demonstrated that the production of DME allows much higher oxygenate yield and selectivity than that of methanol.