To realize the removal of Cu from iron scraps by a segregation during solidification, we demonstrated the Cu segregation in Fe-C-Cu alloy by unidirectional solidification of utilizing a temperature gradient. The effect of cooling rate and initial Cu content of Fe-C-Cu alloy on the segregation behavior of Cu was investigated in the present work. The segregation ratio of Cu between solid and liquid was determined based on the experimental data. We found out that the unidirectional solidification of Fe-C-Cu melts results in the Cu segregation in solidified alloy. The segregation coefficient of Cu was 1.2 for the unidirectional solidification of molten Fe–4.2 mass%C–0.5~3.7 mass%Cu alloy.