Abstract EPR spectra of VO 2+ ions doped in KZnClSO 4·3H 2O single crystals have been studied at different temperatures. The EPR spectrum shows a well-resolved hyperfine and superhyperfine structure patterns. The angular variation of EPR spectra reveals the presence of more than three magnetic complexes, which correspond to distinct sites of VO 2+ ion. From the angular variation EPR data, the spin-Hamiltonian parameters are evaluated and discussed. The optical absorption spectrum studied at room temperature shows bands corresponding to C 4 v symmetry. From the EPR and optical data, the molecular-orbital bonding coefficient ε 2 and β 2 are evaluated and discussed. The observed five-line superhyperfine structure has been attributed to four protons (with I=1/2) from the surrounding water molecules of one of the vanadyl sites.