The selective oxidation of methoxy/methyl-substituted arenes to the corresponding benzoquinones has been first realized using aqueous hydrogen peroxide as a green oxidant, acid tetrabutylammonium salts of the γ-Keggin divanadium-substituted phosphotungstate [γ-PW10O38V2(μ-O)2]5- (I) as a catalyst, and MeCN as a solvent. The presence of the dioxovanadium core in the catalyst is crucial for the catalytic performance. The reaction requires an acid co-catalyst or, alternatively, a highly protonated form of I can be prepared and employed. The industrially relevant oxidation of 3,4,5-trimethoxytoluene gives 2,3-dimethoxy-5-methyl-1,4-benzoquinone (ubiquinone 0 or coenzyme Q0, the key intermediate for coenzyme Q10 and other essential biologically active compounds) with 73% selectivity at 76% arene conversion. The catalyst retains its structure under turnover conditions and can be easily recycled and reused without significant loss of activity and selectivity.