Bis(maltolato)oxovanadium(IV) (abbreviated BMOV or VO(ma)(2)) has been characterized by electron paramagnetic resonance (EPR) spectroscopy in CH2Cl2, H2O, MeOH, and pyridine at both room and low temperatures. Spin Hamiltonian parameters for mono- and bis(maltolato)oxovanadium(IV) complexes [VO(ma)](+) (=[VO(ma)(H2O)(n)](+), n = 2 or 3) and VO(ma)(2) (Hma = 3-hydroxy-2-methyl-4-pyrone, maltol) have been obtained by computer simulation (SOPHE). Configurations of solvated vanadyl/maltol complexes, VO(ma)(2)S, in solution (S = solvent) are proposed on the basis of a comparison of their hyperfine coupling constants with those obtained for related vanadium(IV) compounds in the literature. Whereas at room temperature pyridine coordinates to VO(ma)(2) in a position cis to the oxo ligand (cis isomer), in H2O or in MeOH solvated and unsolvated cis and trans adducts of VO(ma)(2) are all formed, with the cis isomer dominant. As expected, the coordinating ability was found to be in the order py > H2O similar to MeOH > CH2Cl2. In aqueous solutions at room temperature and neutral pH, cis- and trans-VO(ma)(2)(H2O) complexes are present as major and minor components, respectively.