The high undercooling technique by molten glass slag purification and cyclical superheating in Ar atmosphere was applied to bulk Fe-B alloy melts. A hypercooling was achieved which suppressed the formation of stable phase and consequently promoted the nucleation of metastable phase. Fe-17%B and Fe-20%B alloys were investigated, respectively. TEM and X-ray powder diffraction analyses verify the formation of metastable phase in the highly undercooled Fe-B alloy melts. Besides, the critical nucleation work of Fe2B and Fe3B phases was calculated to predict phase selection in the undercooled melts. The results show that the metastable phase formation is a function of the undercooling achieved prior to nucleation. And the amount of undercooling is an important factor in determining microstructural development by controlling phase selection in the undercooled melts.