The characteristics of K, L₁ and L₃-edges XANES spectra of group IV, V, VI compounds, which have different coordination number, number of d-electrons and the symmetry of coordination sphere, have been classified. Two p → d transitions were observed in the second derivative spectra of L₃-edge XANES spectra of all group IV, V, VI compounds. These two transitions can be assigned to split d orbitals. The splitting and area of the two resonances depend on the symmetry of coordination sphere because the splitting corresponds to ligand field splitting of d orbitals. The splitting of d orbitals has a correlation with the pre-edge peak area of K or L₁-edge XANES spectra, which are attributed to the dipole forbidden transition of s → d occurred by mixing of p orbitals with d orbitals. This correlation is supported by DFT calculations of several group IV, V, VI structural models (four-, five- and six-coordinated). The clarification of the correlation between the splitting of the resonance and the structure of group IV, V, VI metal is important to provide structural information in unknown group IV, V, VI metal site.