Six oxidovanadium(V) aroylhydrazone complexes derived from (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H2L1) and (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-aminobenzohydrazide (H2L2), namely, [VOL1(OEt)][VOL1(OEt) (EtOH)] (1), [VOL2(OEt)] (2), [Et3NH][VO2L1] (3), [VO2(HL2)]⋅2 EtOH (4), [(VOL1)2(μ-O)] (5), and [(VOL2)2(μ-O)] (6), were synthesized and characterized by elemental analysis, IR, 1H NMR, and 51V NMR spectroscopies, ESI-MS and, for 1–5, single-crystal XRD. The compounds have VO3+ (1 and 2), VO2+ (3 and 4), and V2O34+ (5 and 6) cores. They are active homogeneous catalysts in the microwave-assisted, solvent-free peroxidative oxidation of 1-phenylethanol to acetophenone by tBuOOH. The immobilization of the oxidovanadium complexes (1, 2, 4, and 5) on oxidized carbon materials improved the oxidation efficiency and allowed catalyst reuse with the preservation of activity.@en