Seven new dioxidomolybdenum(VI) complexes [MoO₂L¹(X)].X (1) and [MoO₂L^2–7(X)] (2–7) [Where X = EtOH in case of 1 and 5 and X = DMSO in case of 2–4 and 6, 7] of aroylazines containing a bulky 3-hydroxy-2-naphthoic substituent, were isolated and structurally characterized. The aroylazine ligands H₂L^1–7 were derived from the condensation of 3-hydroxy-2-naphthoic acid hydrazide with several substituted aromatic aldehydes/ketones. All the synthesized ligands and metal complexes were successfully characterized by elemental analysis, IR, UV–Vis and NMR spectroscopy. X-ray structures of 1–6 revealed that the ligands coordinate to the metal center as a dibasic tridentate ligand. Cyclic voltammetry of the complexes shows two irreversible reductive responses within the potential window −0.50 to −1.36 V, due to Mo^VI/Mo^V and Mo^V/Mo^IV processes. The synthesized complexes 1–7 were used as catalysts for the oxidation of benzoin, and for the oxidative bromination of salicylaldehyde, as a functional mimic of haloperoxidase. It was found that the percentage of conversion increased significantly in the presence of catalysts 1–7 which contained bulky substituents, and showed high percentage of conversion (>90%) with high turnover frequency (>1100 h⁻¹) than previously reported catalysts. Benzil, benzoic acid and benzaldehyde-dimethylacetal were formed selectively for the oxidation of benzoin. Formation of 5-bromosalicylaldehyde and 3,5-dibromosalicylaldehyde took place during the oxidative bromination of salicylaldehyde in presence of H₂O₂ as an oxidant and therefore 1–7 act as functional models of vanadium dependent haloperoxidases.