The evolution process of core-shell microstructures formed in monotectic alloys under the space environment condition was investigated by the numerical simulation method. In order to account for the effect of surface segregation on phase separation, Model H was modified by introducing a surface free energy term into the total free energy of alloy droplet. Three Fe-Cu alloys were taken as simulated examples, which usually exhibit metastable phase separation in undercooled and microgravity states. It was revealed by the dynamic simulation process that the formation of core-shell microstructures depends mainly on surface segregation and Marangoni convection. The phase separation of Fe65Cu35 alloy starts from a dispersed structure and gradually evolves into a triple-layer core-shell microstructure. Similarly, Fe50Cu50 alloy experiences a structural evolution process of "bicontinuous phase → quadruple-layer core-shell → triple-layer core-shell", while the microstructures of Fe35Cu65 alloy transfer from the dispersed structure into the final double-layer core-shell morphology. The Cu-rich phase always forms the outer layer because of surface segregation, whereas the internal microstructural evolution is controlled mainly by the Marangoni convection resulting from the temperature gradient.