Some representative benzylic, aromatic, heterocyclic, carbocyclic and aliphatic hydrocarbons are selectively oxidized in acetonitrile solution medium to their respective aldehydes, phenols, oxides, alcohols and ketones without any over-oxidation to carboxylic acids, in the homogeneous mode using an oxovanadium(V) hydroxamate as catalyst and H2O2 as terminal oxidant. The yield percentage is quite good and the turnover number in each case is highly satisfactory. (C) 2004 Elsevier B.V. All rights reserved.