Anticorrosive properties of borophosphate and boron-free enamels to molten aluminum were investigated using SEM and electron probe. Carbonates of alkali metal and alkaline earth metal were added in an appropriate weight ratio to achieve desired melting temperature of the enamels. SEM examination on the solidified interface between the enamels and aluminum alloy show that the enamels can spread slightly on aluminum alloy. For anticorrosive sample of borophosphate enamel, phosphorus was not detected by electron probe at the side of aluminum alloy near the interface, but silicon was detected in the silica-free enamels side. For the sample of boron-free enamels, however, phosphorus was found at the side of aluminum alloy near the interface. It was revealed that the enamels with high B2O3-P2O5 content have high corrosion resistance to molten aluminum.