A small amount of Hf was employed as a new additive to improve B removal in the electromagnetic solidification refinement of Si with an Al–Si melt, because Hf has a very strong affinity for B. The segregation ratio of Hf between the solid Si and Al–Si melt was estimated to range from 4.9 × 10⁻⁶ to 8.8 × 10⁻⁷ for Al concentrations of 0 to 64 at.%, respectively. The activity coefficient of Hf in solid Si at its infinite dilution was also estimated. A small addition of Hf (<1025 parts per million atoms, ppma) significantly improved the B removal. It was confirmed that the use of an increased Hf addition, slower cooling rate, and Al-rich Al–Si melt as the refining solvent removed B more efficiently. B in Si could be removed as much as 98.2% with 410 ppma Hf addition when the liquidus temperature of the Al–Si melt was 1173 K and the cooling rate was 4.5–7.6 K min^–1. The B content in Si could be controlled from 153 ppma to 2.7 ppma, which meets the acceptable level for solar-grade Si.