A series of 5-coordinate oxidovanadium(iv) complexes based on 2-(2'-hydroxyphenyl)imidazole (HPIMH), with substituent groups of different electronegativities on the phenolic para position (HPIMX; X = -H, -Br, -OMe and -NO2), were synthesized and characterized. Three of these complexes were characterized by single crystal X-ray diffraction, [VIVO(PIMH)2], [VIVO(PIMBr)2] and [VIVO(PIMNO2)2], as well as a dioxidovanadium(v) compound ([VVO2(PIMH)(PIMH2)]). The complexes were tested for their catalytic activities in the oxidation of dibenzothiophene (DBT), the major refractory organosulfur compound found in fuel. The nitro substituted compound [VIVO(PIMNO2)2] had the highest catalytic oxidation activity followed by: [VIVO(PIMH)2] > [VIVO(PIMBr)2] > [VIVO(PIMMeO)2]. The decrease in activity is attributed to the different electronegativities of the substituent groups, which influence the electron density on the metal center, the V[double bond, length as m-dash]O bond distances and infrared stretching bands. Geometry index (τ) values calculated from single crystal X-ray diffraction (SC-XRD) data and DFT studies provided further insights on the trend in activity observed. SC-XRD, EPR, 51V NMR and UV-Vis spectroscopies, and DFT studies were instrumental in studying the mechanism of the catalyzed reaction and proposal of intermediate species. Both radical and non-radical pathways are plausible for the catalytic oxidation and participation of reactive oxygen species in both pathways is also postulated.