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Those peritectic alloys with large positive mixing enthalpy usually display metastable liquid phase separation. Here, the solidification kinetics for a model Fe 50 Cu 50 alloy in broad cooling rate R c range was predicted by phase-field simulations and confirmed by drop tube experiments. Near-equilibrium peritectic solidification occurs in small R c regime below 5.62×10 2 K s −1 . As R c rises beyond 7.76×10 2 K s −1 , metastable phase separation takes place and results in the formation of a dispersed structure. Afterwards, multilayer core-shell structures appear, and the layer-number varies from two-layer to six-layer with further increasing R c . Once R c exceeds 3.64×10 5 K s −1 , a dispersed structure once again forms because the core-shell dynamic condition is not satisfied. Non-equilibrium peritectic solidification is induced if R c is greater than 5.85×10 5 K s −1 . [ABSTRACT FROM AUTHOR]