Efforts have been made aimed at the development of an active active and stable catalyst in the co-production of dimethyl ether (DME) and methanol from CO2–H2. The stabilities of ZSM-5 catalysts and Cu–ZnO-based methanol synthesis catalysts were investigated separately under water-rich conditions. By combining each stable catalyst, a relatively stable hybrid catalyst, Cu–ZnO–Al2O3–Cr2O3 + H–ZSM-5 (SiO2/Al2O3 = 80), has been developed. After losing about 5% of its original activity in 120 h, the catalyst exhibited no significant reduction in activity until 350 h in the reaction at 523 K and 3.0 MPa. Also, the catalytic activity was satisfactory at the steady state: the total yield of DME and methanol was higher than 26% with over 90% DME selectivity, but the total yield of hydrocarbons was lower than 0.25%. Copyright © 2001 John Wiley & Sons, Ltd.