Pure and doped catalysts were prepared with ZnO dopant concentration (0.04–0.08 mol) by wet impregnation method followed by calcination at 350–650 °C. The prepared solids were characterized by X-ray diffraction, N2-adsorption at −196 °C and the methanol conversion as the catalytic probe reaction. The results revealed that the crystallite size and ordering of CuO phase decrease by ZnO-doping for samples calcined at 350–550 °C. Opposite trends were observed by increasing ZnO amount to 0.08 mol (i.e. 9.21 wt%). The specific surface area (S BET) and the catalytic activity of pure catalyst increase by increasing the calcination temperature to 550 °C and/or increasing the amounts of ZnO up to certain extent reaching to a maximum at 7.07 wt% ZnO; above this concentration catalytic activity of doped samples decreases. But at calcination temperature above 550 °C, the catalytic activity and selectivity decrease. The prepared catalysts are selective towards formaldehyde and methyl formate formation.