Under conventional solidification conditions, immiscible alloy melt would undergo large-scale composition segregation after liquid–liquid phase separation, resulting in the loss of properties and application value. In the present study, the ternary immiscible Al70Bi10Sn20 alloy was chosen to study the effect of cooling rate on its resultant microstructure by casting the melt under different cooling conditions. The results indicated that the Al–Bi–Sn alloy with a slow cooling rate exhibits a strong spatial phase separation trend during solidification. However, as the cooling rate increases, the decreasing volume fraction of the segregated Bi–Sn-rich regions indicates the efficient suppression of spatial phase separation. The relatively dispersed distribution of Bi–Sn phase in the Al-rich matrix can be obtained by quenching the melt into water. The influence mechanism of cooling rate on the microstructure of the alloy is also discussed. The present study is beneficial to further tailoring the microstructure of immiscible alloys.