In this work, a novel duplex Ni-P/Ni-Mo-P coating upon the aluminum(Al) substrate was synthesized via an electroless plating, i.e., the binary Ni-P coating as a transition layer and the ternary Ni-Mo-P coating on the top. It was found that the duplex coating was of a high hardness,large elastic modulus,low porosity and excellent corrosion resistance. In addition, experimental results revealed that for a total 20 μm coating thickness, the duplex coating with a 7 μm of the Ni-Mo-P coating exhibited the best corrosion resistance in 0.5 mol/L sulfuric acid solution, which was attributed to its compact structure and low porosity. This duplex Ni-P/Ni-Mo-P coating with a thin ternary Ni-Mo-P layer is expected to solve the problem of low deposition rate of ternary alloy coating and thereby may expand applications of Al and its alloys in the fields of machine manufacture and corrosion environment. In this work, a novel duplex Ni-P / Ni-Mo-P coating upon the aluminum (Al) substrate was formed via an electroless plating, ie, the binary Ni-P coating as a transition layer and the ternary Ni- P was coated on the top. It was found that the duplex coating was of a high hardness, large elastic modulus, low porosity and excellent corrosion resistance. In addition, the experimental results revealed that for a total 20 μm coating thickness, the duplex coating with a 7 μm of the Ni-Mo-P coating exhibited the best corrosion resistance in 0.5 mol / L sulfuric acid solution, which was attributed to its compact structure and low porosity. This duplex Ni-P / Ni-Mo-P coating with a thin ternary Ni-Mo-P layer is expected to solve the problem of low deposition rate of ternary alloy coating and thereby may expand applications of Al and its alloys in the fields of machine manufacture and corrosion environment.