The EPR spectra of VO2+ in Cd(HCOO)2IH2O and Pb(HCOO)2 single crystals and powders were studied at room temperature. The angular variations of the spectra indicated that the VO2+ enters Cd2+ and Pb2+ sites in their respective host crystals. Two magnetically inequivalent sites in Cd(HCOO)22H2O and Pb(HCOO)2 for VO2+ were observed. The principal values of the spin-Hamiltonian parameters g and A were determined from the single crystal and powder EPR spectra. Using the EPR parameters and diffuse reflectance data molecular orbital bonding coefficients and crystal field parameters of VO2+ have been evaluated and discussed. © 1998 Elsevier Science Ltd.