Аннотация:The bis(maltolato)oxo complexes of vanadium(V) and vanadium(IV) both in a soluble form and anchored to chemically modified silica gel, when used in combination with pyrazine-2-carboxylic acid (PCA), catalyze the oxidation of benzene to phenol and alkanes to the corresponding alkyl hydroperoxides with H2O2 at 40–50 °C. Heterogenizing the complexes leads to changes in regioselectivity and bond selectivity parameters of the alkane oxidation, and this opens new routes to the enhancement of the selectivity in oxidation processes.