We her ein rep ort the oxid ative C-C coup ling of k etones and p rimary alcohols to p roduce α,β-unsaturated ketones in the absence of base additives.This cascade synthetic reactions were conducted at 150 oC in 12 h using heterogeneous CeO2 catalyst.The conversion of acetophenone reached 74%with 89%selectivity of chalcone.A correlation between CeO2 crystal plane and catalytic performance is established as the catalytic activities decrease in the sequence of(110)>(111)>(100).The characterizations with Raman spectroscopy,CO2-temperature programmed desorption(CO2-TPD),and in-situ active-site-capping tests have shown that the unusual catalysis of CeO2 catalyst is attributed to the coexistence of basic and redox active sites.These sites synergistically catalyze the oxidation of alcohol to aldehyde and the Aldol condensation to ketones.Moreover,the CeO2 catalyst can be reused for several times after calcination to remove the surface-adsorbed substances.