The effects of Al element addition and partial substitution of Ce with La, Pr, and Nd on the two-glass-forming ability of the phase-separating Zr–Ce–Co–Cu alloy system have been studied. The distribution of the additions in the two coexistent immiscible liquids was analysed thermodynamically. The results indicate that Al almost equally distributes in the two liquids, whereas the elements La, Pr, and Nd are predominantly found in the Ce–Cu-rich liquid. X-ray diffraction analysis reveals that these additions obviously enhance the two-glass-forming ability of the coexisting liquids. This work presents a strategy for improving the two-glass-forming ability of immiscible alloys to obtain phase-separated bulk metallic glasses.