In this paper, Bi-60wt.%Te and Bi-80wt.%Te alloys are selected for experiments to explore the effects of temperature-induced discontinuous liquid–liquid structure transitions TI-LLST on the solidification behaviors and solidified microstructures. Anomalous changes of electrical resistivity of the liquid Bi-60wt.%Te and Bi-80wt.%Te alloys with temperature suggested that TI-LLST occurred within 798–828 and 745–779°C. The solidification results show that solidification behaviors and solidified microstructures of Bi–Te alloys will be apparently distinct when the melt is prepared above the critical temperature. It is found that the nucleation undercooling is larger when the melt experienced the TI-LLST, which leads to finer solidification microstructures.