In this study, a dual amorphous/crystalline nanocomposite coating of Ni–P/Ni–Mo–ZrO2 was designed and successfully deposited on pure copper substrates by pulse electrodeposition. The design of the Ni–P/Ni–Mo–ZrO2 dual coating takes advantage of the properties of the different structures and incorporates second phase reinforcing particles resulting in more comprehensive protective coatings. The surface morphology and microstructure were evaluated by SEM, EDS, WLI, XRD and TEM. The mechanical properties and electrochemical behaviors of the coating in a 3.5 wt% NaCl solution were investigated by wear tests, Tafel and EIS. The results show that the Ni–P/Ni–Mo and Ni–P/Ni–Mo–ZrO2 dual coatings are uniform, dense and crack-free, and the duplex interface is homogeneous. Compared with the Ni–Mo coating, the average friction coefficient and wear rate of the Ni–P/Ni–Mo duplex coating decreased to 0.18 and 5.433 × 10−4 mm3/N·m, respectively. The corrosion potential is positively shifted to −0.43 with a maximum impedance of 308 kΩ cm2. The mismatch of the interlayer defects causes a deviation in the corrosion path, resulting in a transformation from longitudinal pinhole corrosion into extended transverse corrosion, which effectively strengthens the capacity of the coating for corrosion resistance while maintaining the high hardness of its outer coating. Furthermore, the hardness of the dual Ni–P/Ni–Mo coating can be obviously reinforced by nanoparticles from 730 HV to 810 HV, the corrosion potential is shifted to −0.41 V, and the corrosion current density decrease to 7.7803 × 10−7 A/cm2. The improvement in the mechanical properties can be attributed to the ZrO2 nanoparticles, which could carry stress and transfer loads during the wear process. Meanwhile, the ZrO2 nanoparticles can reduce the nodule size by filling the binding boundary which is the main corrosion path, and reduce the number of surface defects, such as pinholes, which leads to a lower corrosion rate. In addition, the corrosion inhibition and nanoparticle codeposition mechanisms of the duplex coatings were further discussed.