Electron paramagnetic resonance (EPR) spectra of VO2+ ions in NaH2PO4 center dot 2H(2)O single crystal have been studied. The spin-Hamiltonian parameters and molecular orbital bonding coefficients were calculated. The angular variation of the EPR spectra shows two different VO2+ complexes. These are located in different chemical environment and each environment contains four magnetically inequivalent VO2+ sites. The crystal field around VO2+ ion is approximately axially symmetric since a strong V=O bond distorts the crystal lattice. Spin Hamiltonian parameters and molecular orbital bonding coefficients were calculated from the EPR data and the nature of bonding in the complex was discussed together. (C) 2016 Elsevier B.V. All rights reserved.