In heterogeneous catalysis processes, development of high-performance acid-base sites synergistic catalysis has drawn increasing attention. In this work, we prepared Mg/Zr/Al mixed metal oxides (denoted as Mg 2 Zr x Al 1- x -MMO) derived from Mg-Zr-Al layered double hydroxides (LDHs) precursors. Their catalytic performance toward the synthesis of diethyl carbonate (DEC) from urea and ethanol was studied in detail, and the highest catalytic activity was obtained over the Mg 2 Zr 0.53 Al 0.47 MMO catalyst (DEC yield: 37.6%). By establishing correlation between the catalytic performance and Lewis acid-base sites measured by NH 3 -TPD and CO 2 -TPD, it is found that both weak acid site and medium strength base site contribute to the overall yield of DEC, which demonstrates an acid-base synergistic catalysis in this reaction. In addition, in situ Fourier transform infrared spectroscopy ( in situ FTIR) measurements reveal that the Lewis base site activates ethanol to give ethoxide species; while Lewis acid site facilitates the activated adsorption of urea and the intermediate ethyl carbamate (EC). Therefore, this work provides an effective method for the preparation of tunable acid-base catalysts based on LDHs precursor approach, which can be potentially used in cooperative acid-base catalysis reaction.