In this work, a significant enhancement of corrosion resistance of Fe-B materials in liquid Al (750 °C), with a corrosion rate one order of magnitude lower than that of H13 die steel, has been achieved by constructing nano-lamellar structures in the matrix. Results indicate that the nano-lamellar structure can not only effectively obstruct the interdiffusion between the Al and Fe atoms, restricting the growth of corrosion layers, but also accommodate sufficient growth and thermal stresses, suppressing the spallation of corrosion products. Furthermore, the ceramic nanoparticles in-situ formed in the nano-lamellar structure can inhibit the inward diffusion of Al atoms, greatly enhancing the corrosion resistance of α-Fe matrix. Besides, they also provide a robust pinning effect on the corrosion interface, improving the adhesion strength of corrosion products with the matrix. The architecture of nano-lamellar structure with nanoparticles may provide a novel strategy against liquid Al corrosion and shed new light on the development of corrosion-resistant materials.