CaO-ZrO2 catalysts were prepared by coprecipitation and their catalytic performances were evaluated in the synthesis of dimethyl carbonate from propylene carbonate and methanol. The characterization by XRD, N-2 adsorption, XPS and CO2-TPD indicated that Ca2+ ion substituted for Zr4+ ions in the host lattice to form homogeneous CaO-ZrO2 solid solution when Ca/(Ca + Zr) ratio changed from 0.1 to 0.3, and CaO segregated at grain boundaries with Ca/(Ca + Zr) ratio from 0.4 to 0.5. As a result, the catalysts showed different activity and stability towards the transesterification of propylene carbonate and methanol into dimethyl carbonate. The activity of catalysts was improved with increase in Ca content. whereas high stability was shown with Ca/(Ca + Zr) ratio below 0.3. The formation of homogeneous CaO-ZrO2 solid solution was responsible for the stability of catalysts. (c) 2006 Elsevier B.V. All rights reserved.