The resistivity versus temperature (ρ-T) behaviours of liquid n-type Bi2Te3-x Se x (x = 0.3, 0.45 and 0.6) alloys are explored up to 1050 °C. A clear hump is observed on all ρ-T curves of the three studied Bi2Te3-x Se x melts during the heating process, which suggests that a temperature-induced liquid-liquid structural transition takes place in the melts. Based on this information, the solidification behaviours and microstructures of the alloys with different liquid states are investigated. The samples that experienced liquid structural transition show that the nucleation and growth undercooling degrees are conspicuously enlarged and the solidification time is shortened. As a result, the solidified lamellae are refined and homogenized, the prevalence of low-angle grain boundaries between these lamellae is increased, and the Vicker Hardness is enhanced. Atom probe tomography analyses prove that there is no segregation or nanoprecipitation within the grains, but the Te-rich eutectic structure and the evolution of composition near the Te-matrix phase boundary are investigated in a sample that experienced liquid structural transition. Our work implies that the solidification behaviours of Bi2Te3-xSex alloys are strongly related to their parent liquid states, providing an alternative approach to tailor the thermoelectric and mechanical properties even when only a simple solidification process is performed.