The reaction between [V^IVOSO₄] and the tetradentate N₂O₂-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [V^IVO(sal-HBPD)]. The molecular structure of [V^IVO(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N₂O₂ binding mode of the tetradentate ligand. The formation of the polymer-supported p[V^IVO(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [V^IVOSO₄]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[V^IVO(sal-AHBPD)] were found to be 6.9 m² g⁻¹ and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [V^IVO(sal-HBPD)] and p[V^IVO(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [V^IVO(sal-HBPD)] and p[V^IVO(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO₂) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO₂) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[V^IVO(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.