The high-phosphorus electroless Ni–P plating coating with 11.64 at.% was prepared by electroless technology. By means of x-ray diffraction and scanning electron microscopy, the morphologies and phase structures of coating were analyzed. Furthermore, the mechanical properties of coating were studied by micro-hardness tester and universal friction-wear testing machine. The results reveal that, with increasing heat-treatment temperatures, the hardness and the wear resistance of the coating are enhanced increasingly. Treated by 1 hour at 500 oC, the hardness and the wear resistance both display a optimum value, i.e. 1004 HV and 1.5×10-3g, respectively. The thermal shock test suggests that between coating and matrix exist a perfect cohesion.