Zn/Al mixed oxides (ZAO) were prepared via thermal decomposition of hydrotalcite-type precursors derived from urea precipitation. Specially, ZAO catalysts with a Zn/Al molar ratio of 4:1 exhibited high dimethyl carbonate (DMC) yield (similar to 36.5%) when utilized for the DMC synthesis from urea and methanol. The XRD, IR, TPD and computational analysis revealed that the formation of ZnAl2O4 spinel significantly modified the surface acidity and basicity of ZAO catalysts, which were beneficial for the DMC synthesis. We thus opened up a hi-functional mechanism that urea and methanol were respectively activated on the weak acidic and basic sites, advancing the DMC synthesis synergistically. (C) 2014 Elsevier B.V. All rights reserved.