The BSE of Co2+ in the three kinds of glass has been observed at 77 K, it is shown that the Co2+ ions are mostly situated on tetrahedral sites. We conclude the order of the effective g value obtained from the experiments is related to a slight change of the chemical bonding nature between the central ions and the ligands. In addition, the ESR of Ni2+ in fluorophosphate glass has been observed and its spectrum is identified. A detailed calculation with the spin-Hamiltonian is carried out, and it explains why the ESR signal of Ni2+ in most oxide glasses can hardly be observed.