Cu-Mn/Ca-Zr catalysts were prepared by mechanical mixing, sol-gel and impregnation methods. The phase structure, surface morphology and the chemical states of catalysts were characterized by XRD, TEM, SEM and XPS. The basic property and reducibility of catalysts were investigated by CO2-TPD and H-2-TPR techniques. Several types of basic sites with different basicity could be observed on the surface of catalysts. The sample prepared by impregnation method has the lowest reducibility, and the sample prepared by sol-gel method shows the highest reducibility. The catalytic performance was evaluated for the direct synthesis of methyl formate from syngas in a slurry phase. The catalyst prepared by mechanical mixing method shows the highest CO conversion of 14.2% and methyl formate selectivity of 83.4% among these catalysts, which could be attributed to the large amounts of strong basic sites and low reducibility of the catalyst. (C) 2016 Elsevier B.V. All rights reserved.