A series of Zn-Al composite oxides that were modified with alkaline earth metals, Zn-M-Al-O ( M = Mg, Ca, Sr, and Ba) were fabricated via calcination of the corresponding hydrotalcite precursors, and evaluated as catalysts for the synthesis of propylene carbonate ( PC) from CO2 and propylene oxide. Among the Zn-M-Al-O catalysts, Zn-Mg-Al-O (Zn/Mg = 4.0, pH = 10, without hydrothermal treatment) is the best in performance, showing PC selectivity of 99.2% and yield of 88.8% (140 degrees C, 12 h). Furthermore, the Zn-Mg-Al-O catalyst can be readily reused and recycled without any loss of activity in a test of five cycles. Through detailed studies of the basic nature of the Zn-M-Al-O catalysts, it was found that a moderate basicity (6.1 <= H-0 < 8.9) is beneficial to the cycloaddition reaction. The NH3- and CO2-TPD results also indicate that the Zn-Mg-Al-O catalyst has acid-base bifunctional properties, and a reaction mechanism is proposed.