Abstract Electron paramagnetic resonance (EPR) of VO 2+ doped potassium hydrogen d-gluconate single crystals and powder have been examined at room temperature. Single crystal rotations in each of the three mutually orthogonal crystalline planes namely ac, ba and ca indicate two different VO 2+ complexes. Each complex is located in different chemical environments, each environment containing two magnetically inequivalent VO 2+ sites in distinct orientations occupying substitutional positions in the lattice and showing a very large angular dependence. The powder spectrum also clearly indicates four different VO 2+ complexes, confirming the single crystal analysis. Crystalline field around the VO 2+ ion is nearly axial. The optical absorption spectrum of VO 2+ ions in the crystal lattice is also studied at room temperature. The characteristic spectrum of the VO 2+ ions has two absorption bonds. The bond positions are at 17 857 and 11 235 cm –1. Spin Hamiltonian parameters and molecular orbital coefficients are calculated from the EPR and the optical data, and results are discussed.