CuZrO2 catalysts were modified with alkaline earth metals Mg, Ca, Sr and Ba as additives, and used to catalyze the one-step preparation of ketones from ethanol. The results showed that the CuZrO2 catalyst modified with alkaline earth metal Ba had higher Cu electron binding energy on the catalyst, which was favorable to the breakage of O-H bonds in ethanol molecules to form acetaldehyde. Thus, the content of desorbed acetaldehyde was the largest on Ba-CuZrO2 catalyst. In addition, the alkalinity of medium strength alkaline site (lattice oxygen) on Ba-CuZrO2 catalyst surface was the strongest, which had a significant promotion effect on the condensation reaction. The selectivity of ketones on Ba-CuZrO2 Catalyst was the highest and the performance of the catalyst was the best. In addition, Ba-CuZrO2 catalyst had a good stability.