A theoretical method for investigating the inter-relation between electronic and the molecular structures of a d 4 ion in a tetragonal ligand-field has been established on the basis of 210×210 complete energy matrix within a weak-field-representation. Using the method, the local structure parameters of CdGa 2 S 4 :Cr 2+ system are determined by the experimental EPR zero-field splitting (ZFS) spectra. Our results show that the local structure around Cr 2+ is a compression distortion and the local lattice structure parameters R=2.46Å and θ=57.63° are determined. Moreover, the contributions of the spin singlets to ZFS parameters of Cr 2+ ions in CdGa 2 S 4 crystals are investigated for the first time. The results indicate that the spin singlets contributions to ZFS parameter D are negligible, but the contributions to ZFS parameters a and F cannot be neglected.