Oxovanadium(IV) complexes of the type [VO(mac)]SO4 (where mac = tetraaza macrocyclic ligands derived by condensation of thenil with 1,4-diaminobenzene or 3,4-diaminopyridine and their reaction with β-diketones) have been prepared using vanadyl ion as kinetic template. The prepared macrocyclic complexes were characterized by elemental analyses, molar conductance, magnetic moments, and infrared, electronic, and electron spin resonance data. From the spectroscopic studies, five-coordinate square-pyramidal geometry for the VO2+ complexes have been proposed wherein derived ligands act as tetradentate chelating agents.