e solidification microstructure evolution of undercooled Cu-15 wt.% Fe alloy melt was studied in this study by the combined method of glass fluxing and overheating. e liquidus and peritectic reaction temperatures of Cu-15 wt.% Fe were experimentally obtained, and the obtained results were consistent with the previous studies. Based on the experimental results and related theories, the solidification process and microstructure evolution of undercooled Cu-15 wt.% Fe alloy melt were illustrated. e conclusions provide the basis to the further study on the liquid-phase separation and application of copper-iron alloy.