Abstract The oxovanadium(II) complexes of the different vitamins like ascorbic acid (vitamin C; Vit. C), riboflavin (vitamin B2; Vit. B2) and nicotinamide (vitamin B3; Vit. B3) were synthesized and characterized by elemental analysis, molar conductance, IR, electronic, magnetic measurements, thermal studies, XRD and SEM. Conductance measurements indicated that the vanadyl(II) complexes of Vit. B2 and Vit. B3 are 1:2 electrolytes except for [VO(Vit. C) 2(H 2O) 2] complex is non-electrolyte. IR data show that Vit. B2 is bidentate ligand against azomethine nitrogen of pyrazine ring and C O of pyrimidine-2,4-dione but Vit. B3 and Vit. C acts as a monodentate ligand through pyridine nitrogen and hydroxo oxygen of furan ring, respectively. Electronic spectral measurements indicated that all VO(II) complexes have a square-pyramidal geometry. Magnetic measurements for the new vanadyl(II) complexes are in a good agreement with the proposed formula. Thermal analyses (TG/DSC) of the studied complexes show that the decomposition process takes place in more than two steps. XRD refer that VO(II) complexes have an amorphous behavior. The surface morphology of the complexes was studied by SEM. The antimicrobial activities of the ligands and its complexes indicate that the vanadyl(II) complexes possess high antibacterial and antifungal activities towards the bacterial species and the fungal species than start ligands.