Phosphorus removal from metallurgical grade silicon by CaO-SiO2-CaCl2 slag treatment, HCl leaching, and vacuum refining was investigated. The effect of different compositions of slag was evaluated. The calcium concentration in slag-treated silicon increased with increasing CaO/SiO2 mass ratio of slag, decreasing the evaporation efficiency of phosphorus in molten silicon. The total phosphorus removal efficiency changed from 93.0% to 98.3% when the slag-treated silicon was treated with HCl before vacuum refining. The final concentration of phosphorus in silicon was 0.43 ppmw. This is because phosphorus was removed from metallurgical-grade silicon as follows: Phosphorus reacts with slag at the silicon/slag interface and forms Ca3(PO4)2 and Ca3P2, most of which diffuse from the interface to the slag phase. The remaining Ca3(PO4)2 and Ca3P2 reduce the phosphorus removal efficiency by altering the activity coefficient of phosphorus in molten silicon. HCl leaching enhanced the phosphorus removal efficiency by removing the remaining Ca3(PO4)2 and Ca3P2. Therefore, the mass transfer of phosphorus from metallurgical-grade silicon was accelerated.