<p>The resource utilization of CO₂ has garnered significant attention. Among various approaches, the direct synthesis of dimethyl carbonate (DMC) from CO₂ is considered an effective route to reduce chemical pollution and achieve atomic economy. In this work, Zr/Sn metal oxide catalysts were prepared by combining the precipitation method with a cotton-templating approach. The mechanistic role of the cotton template in modulating the catalyst structure and its performance in DMC synthesis were systematically investigated. The as-prepared catalysts were characterized by XRD, TEM, SEM, UV-Vis DRS, and Raman spectroscopy to elucidate their morphology, crystalline structure, and optical properties. Furthermore, the structure-activity relationship was established based on catalytic tests. The results indicated that the template agent has a remarkable impact on the structural properties and catalytic activity of the Zr/Sn-2–5&#xa0;g catalyst. The strong interaction between ZrO₂ and SnO₂ facilitates the dispersion and stability of active sites, thereby enhancing the catalyst’s activity and selectivity. Notably, the Zr/Sn-4&#xa0;g catalyst exhibited the highest catalytic activity, yielding 1.74 mmol/g of DMC. This study offers new insights into the design of efficient catalysts for the direct synthesis of DMC from CO₂.</p> Graphical Abstract <p></p>