Phosphorus exhibits considerable segregation in steelmaking slag. In order to recover phosphorus from slag to K3PO4 via molten iron, a carbothermic reaction using microwave heating was suggested recently. The carbothermic reduction of phosphorus from slag to molten iron using microwave heating was carried out at 2073K. However, at this temperature the thermodynamic properties of both slag and molten iron cannot be determined experimentally. Therefore, the computational approach of the so-called CALPHAD method is very useful to understand the transfer of phosphorus from slag to metal and to enhance this reaction. In the present investigation, a theoretical study of the reduction behavior of phosphorus in slag was carried out at much lower temperatures using the recently developed thermodynamic database in the FactSage program. The calculated results showed reasonable accordance with the experimental data; namely, the thermodynamic database could be applied successfully to higher temperature reactions. The current study found that higher temperature and high SiO2 concentration are favorable for the recovery of phosphorus from slag.