The conversion of CO₂ to dimethyl carbonate (DMC) represents a promising route for sustainable synthesis and carbon resource utilization. In this study, a series of Zr-doped CeO₂ catalysts derived from metal–organic frameworks (MOFs) via hydrothermal synthesis were applied to the direct synthesis of DMC from CO₂ and CH₃OH. The effects of varying Zr doping levels (molar fraction, the same below) on catalytic performance were systematically investigated, and the optimal Zr doping amount was determined. The catalysts were characterized using X-ray diffraction, high-resolution transmission electron microscopy, N₂ adsorption-desorption, and X-ray photoelectron spectroscopy to elucidate their crystal phase, morphology, surface chemical states, and correlations between these properties and catalytic activity. Using the Zr/CeO? catalyst with a 2% Zr doping level, the optimal process conditions for DMC synthesis from CO? and CH?OH were investigated. The results indicate that under the conditions of 140 °C, an initial CO₂ pressure of 3 MPa, and a reaction time of 2 hours, the Zr/CeO₂ catalyst with a 2% Zr doping content exhibits the highest CH₃OH conversion rate and DMC production.