Abstract: This study investigates a purification process for metallurgical-grade silicon (MG-Si) in which Si is alloyed with tin (Sn) and CaO-SiO₂-CaCl₂ slag is used to remove boron (B) impurity. Acid leaching was performed to remove the Sn phase after slag refining to recover high-purity Si from the Si-Sn alloy. The effect of refining time was investigated, and acceptable refining results were realized within 15 min. The effects of slag composition and Sn content on the removal of B were also studied. The results indicate that increasing Sn content favors B removal. With the increase of Sn to 50% of the alloy, the final B content decreased to 1.1×10^-4wt%, 93.9% removal efficiency.