During the interfacial reaction between novel Fe-Cr-B cast steel and molten aluminum the formation of a periodic layered structure was observed at the Cr-rich Fe2B/Al interface. The periodic layered structure was investigated by scanning electron microscopy and electron probe micro-analyzer. It was embedded in the Fe-Al intermetallics (reaction productions of the Fe substrate). Cr element had a key influence on the formation of PLS. A model describing the formation of periodic layered structure between novel Fe-Cr-B cast steel and molten aluminum is presented.