A large undercooling (250 K) was achieved in eutectic Ni78.6Si21.4 melt by the combination of molten-glass denucleation and cyclic superheating. The metastable phase formation process in the bulk undercooled eutectic Ni78.6Si21.4 melts was investigated. With the increase of undercooling, different metastable phases form in eutectic Ni78.6Si21.4 melts and part of these metastable phases can be kept at room temperature through slow post-solidification. Under large undercooling, the metastable phases β2-Ni3Si, Ni31Si12 and Ni3Si2 were identified. Especially, the Ni3Si2 phase was obtained in eutectic Ni78.6Si21.4 alloy for the first time. Based on the principle of free energy minimum and transient nucleation theory, the solidification behavior of melts was analyzed with regard to the metastable phase formation when the melts were in highly undercooled state.