<p>A series of Zn_xCe_1-xO₂ catalysts with different Zn/Ce molar ratios were prepared using the co-precipitation method and used for the synthesis of diethyl carbonate from carbon dioxide and ethanol. The catalysts were characterized by XRD, SEM, N₂ adsorption–desorption, XPS, Py-IR, NH₃-TPD and CO₂-TPD. Characterization results revealed that the optimal density of acid–base sites (with Lewis acids as the dominant species) was achieved at a Zn/Ce molar ratio of 0.1. The introduction of ZnO promotes the formation of Ce³⁺ and leads to a significant increase in the number of Lewis acid sites. ZnO doping induces lattice distortion in CeO₂ and generates abundant oxygen vacancies, which in turn promotes the reduction of Ce⁴⁺ to Ce³⁺ and thus optimizes the distribution of acid–base pairs. Ethanol and CO₂ first form an ethoxycarbonate intermediates at the acid–base sites of the catalyst, which then further reacts to produce DEC. Under conditions of 170&#xa0;°C, 4.5&#xa0;MPa, and 3&#xa0;h, the Zn_0.1Ce_0.9O₂ catalyst showed excellent catalytic activity. The yield of DEC was 4.32 mmol_DEC g_cat⁻¹, 32% higher than that of pure CeO₂. The catalyst offers advantages such as simple preparation process, low cost, and no need for dehydrating agents, which provides support for its large-scale industrial application.</p>