The growth in the solar energy technology caused inshortage solar grade Si. As a lowcost, environmental friendly technology, metallurgical method purity silicon is developed significantly. However, as a typical impurity in Si, B is difficult to be removed by directional refining or vacuum melting due to its large segregation coefficient and less evaporation coefficient. In this paper, the big difference of evaporation pressure between Si and B can be applied to separate B from Si, in which, B is remained in molten Si, while most of Si becomes evaporant. Electron beam is applied to scan molten Si and the Si existed in the form of the evaporant is gather on the watercooled crystallizer. The content B in the evaporant is undetectable by ICP-MS.