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Immiscible alloys have been investigated as a kind of alloys with special metallurgy characteristics. Liquid phase separation of Al-Bi immiscible alloys has been investigated for decades. In this work, the microstructure and the wear resistance of Al-Bi-Ce-Cu alloys were investigated. The intermetallic compounds Bi₂Ce form and act as heterogeneous nucleation sites of Bi-rich droplets, which promote the nucleation of Bi phase and obtain a dispersed microstructure. The intermetallic compound Al₂Cu locate in the Al-rich matrix and enhance the hardness of matrix. The wear resistance of alloys is not only dependent on the size of Bi-rich droplets but also dependent on the hardness of matrix. The refined microstructure and the strengthened hardness improve the wear resistance of Al-Bi alloys. Therefore, Al-Bi-Ce-Cu immiscible alloys is useful as a wear resistance material.