Vanadium catalysts supported on N-doped carbon materials (CN) were prepared and the catalyst VOSiW showed high activity for the hydroxylation of various aromatics with O-2. Aromatics with electron-withdrawing groups such as CN, NO2, COOH, CF3, COCH3 and aromatic halides (F, Cl and Br) were oxygenated to the corresponding phenols in considerable yields. The CN materials were not only indispensable for the reusability of the vanadium catalyst VOSiW, but also favorable to the high catalytic activity. The VOSiW catalyst is ready for the hydroxylation of aromatics with O-2 as both V4+ and V5+ species are coexisted in the VOSiW catalyst.