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Ni–P(–SiC) composite coatings were successfully deposited on 70 vol% SiCp/Al composite by electroless plating. The surface microstructures and the phase structures of the Ni–P(–SiC) coatings were examined and analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD) before and after heat-treatment at 200–400 °C for 2 h. The thermal diffusivity of the deposited samples and the interface adhesion between the coating and the substrate were investigated. The experimental results show that SiC content in the coatings increases obviously and XRD peaks are enhanced with SiC content in the bath increasing from 3 to 9 g·L−1. After heat-treatment, the surface of the coating becomes smoother and no diffusion layer is produced at the interface. A new phase Ni3P forms in the coating during heat-treatment at 400 °C. The critical load (Lc) of Ni–P–SiC composite coating on SiCp/Al composite reaches the maximum value of 84.9 N with SiC content of 3 g·L−1 after heat-treatment at 200 °C and more or less decreases with the increase in SiC content and heat-treatment temperature. The thermal diffusivity of deposited samples gradually increases as the temperature increases; however, it reduces firstly and then climbs with the increase in SiC content. [ABSTRACT FROM AUTHOR]