The effects of melt overheating treatment on solidification of Pb-Bi alloys were studied from the viewpoint of liquid-liquid structure change (LLSC). Anomalous temperature dependence of internal friction, electrical resistivity, and entropy of liquid Pb-Bi alloys suggested that discontinuous LLSC occurred within about 520–740 °C, based on which the solidification experiments were carried out with different states of Pb-Bi melts. The results revealed that the LLSC affected the solidification behavior and microstructures significantly, that is, the enlarged undercooling, increased nucleation rate, and refined and improved morphologies were brought about when solidifying from the melt experienced LLSC. It is assumed that the LLSC changed the energy constitution of the melt system, and further affected the effective partition coefficient, thermodynamics, and kinetics of crystal growth, then finally altered the solidification behavior and solidified microstructures. This work brings a novel insight into the effect of melt overheating treatment on solidification, by which it could be more effective to manipulate melts.