<p>Direct synthesis of dimethyl ether (DME) from carbon dioxide (CO₂) hydrogenation by using bifunctional catalysts has attracted much attention in view of CO₂ conversion and utilization. However, direct CO₂ hydrogenation to DME is challenging due to kinetics and thermodynamic limitations, thus requiring the development of more effective bifunctional catalysts. In this work, metal-organic framework (MOF) Cu/Zn-BTC derived CuZnO catalyst is developed and combined with HZSM-5 for direct CO₂ hydrogenation to DME. The influence of Si/Al ratio of HZSM-5, mass ratio of CuZnO and HZSM-5, reaction temperature, reaction pressure and space velocity on the catalytic performances of the CuZnO/HZSM-5 bifunctional catalysts is systematically examined in a fixed-bed reactor. Attributing to a high activity of the Cu/Zn-BTC derived CuZnO catalyst for CO₂ hydrogenation to methanol, the CuZnO/HZSM-5 bifunctional catalysts display high CO₂ conversion and DME selectivity. Under a mild reaction condition (225&#xa0;°C and 3.0&#xa0;MPa), a high CO₂ conversion of 54.3% and DME selectivity of 79.5% are obtained for the bifunctional catalysts, which outperform the state-of-the-art catalysts for CO₂ hydrogenation to DME. Further, after 100&#xa0;h of reaction, the bifunctional catalyst can still maintain a high CO₂ conversion rate (~ 52.6%) and DME selectivity (~ 77.3%), which suggests promising prospects for industrial applications.</p>