Since the contribution of the spin-orbital coupling interaction of the ligand to optical and electron paramagnetic resonance (EPR) spectra can not be neglected, the optical and EPR spectra (g factors g‖、g⊥ and hyperfine structure constant A‖、A⊥ of LiHSO4:VO2+ crystal are calculated from the high-order perturbation formulas on the basis of double-spin-orbital coupling model and crystal-field theory for 3d1 ion in tetragonal symmetry. The calculated results are in good agreement with the observed values. Since the EPR parameters are sensitive to the local structure of a paramagnetic impurity center, the defect structure of V4+ center in LiHSO4 crystal is obtained. The validity of the results is discussed.