Applying crystal field theory and irreducible representation method,the completely diagonalized Hamiltonian matrices of 3d2/3d8 ion configurations in the trigonal symmetry sites are established,which includes four kinds of microscopic magnetic interactions:spin-orbit interaction,spin-spin interaction,spin-other-orbit interaction and other orbit-other orbit interaction.The spectral fine structure,local structure and zero-field splitting parameters of V3+∶α-Al2O3 and Ni2+∶α-Al2O3 crystals are investigated as well as the influence of the doping.The results show that doping complementary ions can not change the fine structure of spectra and the symmetry of crystal structure but the spectral splits and local structure of crystal.The local structure stretch distortion in Ni2+∶α-Al2O3 is larger than that of V3+∶α-Al2O3 crystal while the angle change is less.