Inspired by its role in inducing electroless iron plating, aluminum was used to prepare iron coatings on copper substrates from the simple plating bath containing no reducing agents. The electrochemical investigation indicated that the coupled aluminum could shift the potential of copper substrates to an enough negative value to initiate iron plating in the alkaline plating bath and serve as the electron source for continuous deposition of iron. To improve the corrosion resistance of the iron coatings, graphene oxide (GO) was added in the former plating bath and the iron-reduced graphene oxide (Fe-rGO) composite coatings could be successfully obtained. Compared with the iron coatings, the Fe-rGO coatings exhibited smaller nodule size and denser structure as revealed by scanning electron microscope and X-ray diffraction results. Hence, Fe-rGO coatings demonstrated significant improvement in the corrosion resistance with increasing in open circuit potential (OCP) and reducing in corrosion current density.