The metallurgical behavior of adjusted converter slag components during the selective reduction process were investigated by thermodynamic calculating with different modified slag composition, addition of reducing agent and reduction temperature. The activities of main slag components were drawn from the calculated values. The results showed that the activity of SiO2 increased with increment of its mass fraction in slag. The solubility of SiO2 increased with increment of temperature. The selective reduction was promoted by selecting the appropriate amount of modifier. Reduction order was elucidated in this paper, Fe was reduced from the slag followed by P, Mn and Si and the reduction rate of Si could reach about 51%. The metal phase was rich in Fe, Si, Mn and P as a result of the selective reduction.