New dioxidomolybdenum(VI) complexes, [Mo^VIO₂{Hdfmp(bhz)₂}(MeOH)] 1, [Mo^VIO₂{Hdfmp(inh)₂}(MeOH)] 2 and [Mo^VIO₂{Hdfmp(nah)₂}(MeOH)] 3 of ligand H₃dfmp(L)₂I, are obtained by the condensation of 2,6-diformyl-4-methylphenol (dfmp) and hydrazides (L) [L = benzoylhydrazide (bhz), isonicotinoylhydrazide (inh), and nicotinoylhydrazide (nah)], respectively. All these complexes are characterized in the solid state and in solution namely by elemental analyses, spectroscopic techniques (IR, electronic, ¹H and ¹³C NMR) and thermogravimetric analyses. Single crystal X-ray analysis of complexes 1 and 3 confirms the coordination of the ligand in the dianionic (ONO²⁻) enolate–tautomeric form and one of the hydrazido moieties remains non-coordinated. Oxidation of secondary alcohols: 1-phenyl ethanol, 2-propanol and 2-butanol, catalyzed by these molybdenum complexes, using conventional liquid phase and microwave-assisted methods in the presence of 30% H₂O₂ as an oxidant has been tested. The effects of various factors, such as temperature and amounts of catalyst, H₂O₂ and solvent have been investigated. These alcohols under the optimized reaction conditions gave high yields of the respective ketone. Addition of an N-based additive reduces the reaction time considerably. Amongst the two methods studied, the microwave technique proves to be a time efficient system.