XNiO/CeO2(0.7)-ZnO(0.3) (X = 0, 1, 5, 10, and 15) nano-catalysts were prepared by a wet impregnation method with a variation of NiO content (X, wt%). The prepared catalysts were then applied to the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. Successful formation of XNiO/CeO2(0.7)-ZnO(0.3) nano-catalysts was confirmed by XRD and ICP-AES analyses. Acidity and basicity of XNiO/CeO2-ZnO were measured by NH3-TPD (temperature-programmed desorption) and CO2-TPD experiments, respectively, with an aim of elucidating the effect of acidity and basicity of the catalysts on the catalytic performance in the reaction. It was revealed that the catalytic activity of XNiO/CeO2(0.7)-ZnO(0.3) was closely related to both acidity and basicity of the catalysts. The amount of dimethyl carbonate produced over XNiO/CeO2(0.7)-ZnO(0.3) increased with increasing acidity and basicity of the catalysts. Thus, both acidity and basicity of the catalysts played important roles in determining the catalytic performance in the direct synthesis of dimethyl carbonate from methanol and carbon dioxide.