Abstract: The extended-Huckel molecular orbital approach has been applied to a calculation of the electronic structures of the Te₆⁴⁺and Pf₆^4-ions. The difference of the bonding property between Te₆⁴⁺, Pf₆^4-and prismane, benzene with the same configuration has been studied by the coefficients and energy levels of their occupied molecular orbitals. It is shown that the weak antibonding orbitals with slightly higher energy level than p orbitals of the free atom Te and Pare occupied by their extra valence electrons of Te₆⁴⁺and Pf₆^4-. The interpretation of the stability of the Te₆⁴⁺and Pf₆^4-ions was proposed.