Four new oxovanadium(IV) compounds were prepared by template reaction of salicyl-, 5-bromosalicyl-and 3-methoxysalicyl-aldehyde S-methylthiosemicarbazones with 2-hydroxy-, 5-bromo-2-hydroxy-and 3-methoxy-2-hydroxy-benzaldehyde in various combinations. The compounds were isolated as stable solid compounds with general formula [VO(L)] and characterized by elemental analysis, conductivity and magnetic measurements, electronic, IR and EPR spectroscopy. The X-band EPR signals recorded from powder forms of all samples have a single asymmetric line shape and theoretical fit studies proved the presence of axial symmetry around the paramagnetic vanadium ions. The anisotropic Lande splitting factors take values of g‖ < g⊥ < ge = 2.0023. Orbital energy levels for magnetic electrons were determined from theoretically well fitted Spin Hamiltonian parameters. The EPR spectra recorded from solution forms almost have isotropic character.