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In this study, the Al75Bi20Cu5 monotectic alloy was prepared by a rapidly copper-cooling method. The effect of cooling rate on the melt structure transition and solidification behavior of Al75Bi20Cu5 monotectic alloy, as well as the formation mechanism of core-shell structure of the Al75Bi20Cu5 alloy were investigated. The phase composition of the Al75Bi20Cu5 monotectic alloys was analyzed by EDS, and the thermodynamics and phase transition behavior of Al75Bi20Cu5 monotectic alloy were studied by means of DSC and resistivity measurement. It was found that the Al75Bi20Cu5 alloy cast into the copper mold with an ingate radius of 2 mm finally obtained an egg-type core-shell structure. Keywords: Monotectic alloy, Cooling rate, Liquid-liquid phase separation, Core-shell structure