A Mn promoter was introduced into a Cu-Cr-Zr composite oxide catalyst for the direct synthesis of ethyl acetate from ethanol dehydrogenation by means of coprecipitation method. The effects of the Mn promoter on the structure and catalytic performance of the catalyst were investigated with characterization techniques including XRD, TPR, XPS, and N2O TPD. An interaction between the Mn promoter and the CuO in the catalyst was found to exist, and it improved the dispersion of the Cu component on the catalyst surface and decreased the size of CuO crystal particles, thereby increasing the thermal stability of the catalyst. The results of long-duration activity tests indicated that the Mn-promoted CCZ (Cu-Cr-Zr) catalyst maintained its activity and showed good stability.