A series of CuNiAl hydrotalcites (HTs) were prepared and used to the selective oxidation of glycerol with O-2. The results revealed that elemental composition, structures and the surface properties of the obtained catalysts significantly influenced their catalytic performance. Among them, amino-functionalized CuNiAl-HTs showed excellent catalytic performance due to their enhanced surface Lewis basicity. Under the optimal reaction conditions, the highest conversion of glycerol reached 68.1% with 76% of the selectivity to glyceric acid; moreover, the catalytic performance remained after being recycled 6 times. (C) 2013 Elsevier B.V. All rights reserved.