For two main Jahn-Teller distortion modes of the divacancy in Si, hyperfine interactions of the unpaired electron of both negative and positive charged states (V2-,V2+) are calculated by using extended Koster-Slater model. The calculated results in agreement with the experiments are obtained., From these, we determe that the unpaired electron of V2+ is located at the symmetric state Ag of the energy level at 0.3eV and the V2- is located at the symmetric state Bu of the energy level at 0.63eV. We infer that the EG1 mode is the preferential mode of distortion for both V2- and V2+.