The magnetic exchange interaction behavior and energy spectrum of low-lying spin states are investigated by using ab initio multireference configuration-interaction method for the representative binuclear transition-metal complexes fsNH3d5Crs m-OHdCrsNH3d5g5+ and fCl3FeOFeCl3g2−. Our calculations for the nonmodeling real title complexes found that under the appropriate basis sets and active space, ab initio method at multireference configuration-interaction level of theory is able to give accurate energy spectrum of low-lying spin states within reachable computation demand nowadays and the deviation of magnetic exchange interaction to Lande interval rule can be described by the biquadratic correction in terms of Heisenberg spin Hamiltonian. As a methodology comparison, density-functional theory combined with broken-symmetry approach provides an alternative yet efficient approach to produce accurate numerical results, but there are dependences on the particular chosen exchange-correlation functionals and system dependent. The spin population analyses at complete active space self-consistent-field level of the theory provide an instructively understanding and prediction for the magnetic interaction mechanism.