High undercooling (about 392 K) was achieved in the bulk eutectic Ni_(70.2)Si_(29.8) alloy melt through glass fluxing combined with cyclic superheating. It is found that the metastable phases Ni_3Si_2 and NiSi are obtained through slow post-solidification when undercooling exceeds 240 K. The metastable phases are confirmed by using the method of X-ray diffraction and differential scanning calorimetry (DSC). Based on the principle of the free energy minimum and the transient nucleation theory, the phase selection of melt is investigated with regard to the metastable phases formation in the bulk undercooled eutectic Ni_(70.2)Si_(29.8) melts. The formation of metastable phases from undercooled Ni_(70.2)Si_(29.8) melts is ascribed to competitive nucleation with the undercooling, I.e. High undercooling facilitates the pref-erential nucleation of metastable phases.