It is of great significance to develop an inexpensive and efficient catalyst to enhance the catalytic activity of oxidation coupling of alcohols with amines to imine. In this research, a series of manganese-iron bimetallic oxide catalysts have been prepared by a simple co-precipitation method, which were applied to the catalytic reaction of oxidation coupling of benzyl methanol with aniline to N-benzylideneaniline. The effects of different Fe/Mn feed ratios on the catalytic activity of the products have been explored. The Mn_0.5Fe_0.5O_x sample with a Fe/Mn feed ratio of 1:1 demonstrated the best catalytic activity, giving an aniline conversion rate of 74.7%, 99.9% selectivity and 74.6% yield of N-benzylidene, respectively. Through a variety of characterizations, Mn_0.5Fe_0.5O_x exhibited rich mesoporous structure and surface adsorbed oxygen species, as well as excellent oxidation ability. The high-efficiency catalyst synthesized in this work has great application potential in the preparation of imines by oxidation coupling of alcohols with amines.