The thermodynamics of phosphorus in molten Si-Fe and Si-Mn alloys has been investigated at 1723 K by equilibrating the alloys in a controlled phosphorus partial pressure. The activity coefficient of phosphorus in each alloy shows a maximum value at a certain composition due to a strong interaction between silicon and iron and between silicon and manganese. Interaction coefficients between phosphorus and iron in molten silicon were found to be e P Fe =7.43 and ρ P Fe =−16.4 (0≦X Fe≦0.65), and those between phosphorus and manganese were e P Mn =12.0 and ρ P Mn =−22.2 (0≦X Mn≦0.5). Further discussion has revealed that the Si-Fe-P and Si-Mn-P systems approximately conform to a regular solution within the composition ranges investigated in the present work.