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A novel template-free oxalate route was applied to synthesize different mesoporous manganese oxides (amorphous manganese oxide (AMO), Mn5O8, Mn3O4, MnO2) in the narrow temperature range from 350 °C to 400 °C by controlling the calcination conditions, which were employed as the efficient catalysts for the oxidative coupling of alcohols with amines to imines. The chemical and structural properties of the manganese oxides were characterized by the methods of thermogravimetry analysis and heat flow (TG-DSC), X-ray diffraction (XRD), ni-trogen sorption, scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelec-tron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR), and inductively coupled plasma optical emission spectrometry (ICP-OES) techniques. The structures of different manganese oxides were con-firmed by characterization. The M-350 (AMO) presented the maximum surface area, amorphous nature, the low-est reduction temperature, the higher (Mn3++Mn4+)/Mn2+ratio, and the higher adsorbed oxygen species compared to other samples. Among the catalysts, M-350 showed the best catalytic performance using air as an oxidant, and the conversion of benzyl alcohol (BA) and the selectivity of N-benzylideneaniline (NBA) reached as high as 100％and 97.1％respectively at the lower reaction temperature (80 °C) for 1 h. M-350 had also the highest TOF value (0.0100 mmol·mg?1·h?1) compared to the other manganese oxide catalysts. The catalyst was reusable and gave 95.8％conversion after 5 reuse tests, the XRD patt of the reactivated M-350 did not show any obvious change. Lattice oxygen mobility and (Mn3++Mn4+)/Mn2+ratio were found to play the im-portant roles in the catalytic activity of aerobic reactions.