In this contribution, the selective oxidation of benzyl alcohol using molecular oxygen over supported manganese and vanadium catalysts was investigated. The catalytic activities were significantly improved after pre-oxidizing the activated carbon support materials. Characterizations of nitrogen physisorption, X-ray diffraction, transmission electron microscopy, and X-ray absorption were involved to examine the physicochemical properties of as-prepared catalysts. By ruling out the effects of specific surface area, active site dispersion, valence and local coordination of Mn and V active species, the improved catalytic activity was attributed to the specific variety and increased density of oxygen-containing groups on activated carbon support surfaces, which was further confirmed by cyclic voltammetry measurements and Fourier transform infrared spectroscopy.