Vanadium complexes with polydentate heteroligands providing an NO donor set have been used to mimic structural function and catalytic reactivity for vanadium-containing enzymes such as haloperoxidase, and some of them have been shown to catalyze the oxidation of hydrocarbons by using peroxides as oxygen atom donors. We have also reported the synthesis and structural characterization of a new five-coordinate square pyramidal dialkoxo-bound monooxo-vanadium(V) complex and its behavior in solution. In addition, this complex was found to efficiently catalyze allylic alcohol oxidation with cumene hydroperoxide as an oxidant. In particular, solvent has an influence on the conversion and product selectivity.