A novel aluminum bronze over the Cu-Al binary alloy eutectoid Cu-14Al-4.5Fe was prepared by a jointly-charging one-melting technique and conventional sand casting. The bronze coatings were atmospherically plasma sprayed on the 45# medium carbon steel substrate. The effect of rare earth Ce on the microstructures and Vickers hardness of the cast alloy and coatings were characterized by scanning electron microscopy, X-ray diffraction, electronic probe microanalysis, transmission electron microscopy and microhardness measurements. The results indicate that the hardness of both as-cast alloy and coating are enhanced by the addition of 0.6% Ce due to the refinement of κ phases which are well distributed in the matrix. The rapid solidification in the plasma spray processing retains Fe-supersaturated in the Al-bronze alloy coatings, which avoids the formation of eutectoid (α+γ2) phase and stacking faults are found in the coatings with Ce added, accordingly improves the mechanical properties.