<p>This study investigated the effect of metal dopants on the surface properties of ZnO-based catalysts for the transesterification of propylene carbonate (PC) with methanol to produce dimethyl carbonate (DMC). A series of metal-doped ZnO nanocatalysts (M-ZnO, where M is Ca²⁺, Cu²⁺, Ce³⁺, La³⁺, and Y³⁺ with the mol ratio of Zn²⁺/M^x+  = 4) were prepared by a simple co-precipitation method followed by calcining in air at 673&#xa0;K for 5&#xa0;h. Introducing different metal cations into the ZnO system decreased crystallite size and created surface defects of exposed cations and oxygen vacancies, increasing surface-active acid and basic sites. The catalytic performance for DMC production was ranked as follows: Ca-ZnO &lt; Cu–ZnO &lt; ZnO &lt; Ce-ZnO &lt; Y-ZnO &lt; La-ZnO. La-ZnO showed the highest performance of all catalysts, with 67% PC conversion, 67% DMC selectivity, and 45% DMC yield. The improvement of catalytic activity was correlated with an increase in the concentration of moderate and strong acid–base functionalities on the La-ZnO surfaces for participating in the reaction of PC and methanol to form DMC.</p> Graphic abstract <p></p>