Al/Fe bimetals prepared by a compound casting method, combining the excellent properties of both the Al alloy and the ductile cast iron, exhibit great potential for application in achieving engine weight reduction. However, the problem of insufficient interfacial bonding ability because of the difference in thermophysical properties of Al and Fe is particularly prominent. Therefore, in this work, the electrodeposited Cu coating on the surface of the Fe matrix was used as the interlayer of Al/Fe bimetal fabricated by coupling hot-dipping with compound casting to solve the above problem. The effect of Cu interlayer thickness on the interfacial microstructure and shear strength of bimetal was investigated. The experimental results showed that the shear strength up to 77.65 MPa in regard to Al/Fe bimetal with a 5 μm Cu interlayer was obtained. No Cu element was detected at the interface of bimetal regardless of the thickness of the Cu interlayer. The diffusion behavior of the Cu atom at the interface and the influence of the Cu layer at the atomic scale on diffusion reaction and the Al/Fe interface were further revealed by combining first-principle and molecular dynamics calculations. The simulation results revealed that the Cu layer gradually dissolved into an Al alloy at 750 °C, thereby promoting the diffusion reaction of the Al/Fe interface. Meanwhile, the protective role of the Cu layer against oxidation on the surface of the Fe matrix was confirmed. As a result, the interfacial bonding performance was enhanced when the Cu interlayer was introduced.