Since the spin-orbit coupling parameter (ζ0p≈150 cm-1) of ligand O2- is close to that (ζ0d≈248 cm-1) of the central 3d1 ion in Zn(antipyrine)2(NO3)2:VO2+ crystal, the effect of the spin-orbit coupling parameter ζ0p on the electron paramagnetic resonance (EPR) spectra and optical absorption spectra should be taken into account. Therefore, the EPR spectra and optical absorption spectra of VO2+ in Zn(antipyrine)2(NO3)2 single crystal are calculated based on the two-spin-orbit-coupling parameter model and correlative formulae of the crystal-field energy levels. Theoretical results of EPR spectra and optical absorption spectra of Zn(antipyrine)2(NO3)2:VO2+ are in good agreement with experimental findings. According to the present investigation, the value of this tetragonal distortion of the local symmetry along C4 axis is 0.45 nm. The calculated result shows that the large value of κ indicates a large contribution to the hyperfine constant by the unpaired s-electron. The reasonableness of these results is discussed.