The interfacial reactions of molten Sn and molten In with solid Cu substrate were determined by studying their reaction couples. The annealing temperature was 300 ЊC. The phases formed at the interface were examined by optical microscopy, scanning electron microscopy, and electron probe microscopy analysis (EPMA). The thickness of the reaction layers was measured using an image analyzer. For Cu/Sn couples, two phases, ε and , were found. Only the Cu 11 In 9 phase was observed at the interface of the Cu/In couples. In comparison with the results of couples of solid Sn and solid In with solid Cu substrate, their phase formation sequences were similar; however, the interfacial morphology and the reaction rates were different. For the liquid/solid couples, the reaction rate was much faster and the interface was nonplanar. A mathematic model was also proposed to describe the dissolution of the Cu substrate and the growth of the intermetallic compounds. Fast dissolution of the substrate was observed in the beginning of the reaction and was followed by a relatively slow growth of the intermetallic compounds at the interface.