Cu/Fe multilayered laminated composite was fabricated by a repeated diffusion-rolling procedure. With diffusion bonding initially, thinner layer was fabricated by rolling, and this procedure was repeated. The evolution of structure and properties of Cu/Fe multilayered composite was investigated. The low inter-solubility interface was examined by using high angle annular dark field (HAADF) imaging mode in scanning transmission electron microscopy (STEM). The interfacial strength of Cu/Fe was enhanced by the plastic deformation after rolling. Parallelism of interfaces can almost be achieved when the thickness of layer is above 25 μm or total reduction ratio is lesser than 99%. An inter diffusion area with about 25 nm in width was present at the interface. HR-TEM and FFT investigations at the interface region revealed that disordered substitutional solid solution of Cu and Fe occurred during the procedure.