Firstly, mullite powders were Ni-P plated by electroless plating, and next, subjected to a heat treatment at 850℃. Then coatings of blank- and Ni-P plated-mullite powders were plasma sprayed on 304 stainless steel, respectively. The friction and wear properties of the coatings at 800℃ were tested by a tribometer. The Ni-P plated powders and the plasma spraying coatings were characterized by means of SEM, XRD and Vickers microhardness tester. The results show that the optimized process parameters for electroless plating were as follows: the bath with pH 5.5 composed of NiSO₄·6H₂O 20 g/L, NaH₂PO₂·H₂O 30 g/L, Na₃C₆H₅O₇·2H₂O 20 g/L and NH₄Cl 20 g/L, the plating was conducted at 80℃for 1 h. The plated Ni-P layer on the surface of mullite powder was uniform and compact, and the heat treatment made the layer change from amorphous to crystalline consisted of Ni and Ni₃P. The sprayed mullite coating was mainly composed of mullite phase and γ-Al₂O₃ phase, and the sprayed coating of Ni-P plated powders was mainly composed of Ni, AlNi₃, Ni₃P and mullite. The introduction of Ni-P plating for mullite powders could enhance the hardness of the sprayed coating from 417.5 HV_0.2 to 500.1 HV_0.2. The sprayed coating of Ni-P mullite powders presented a good wear resistance superior to that of the blank ones. Correspondingly, the Ni-P plated powder coating has significantly lower friction coefficient with a wear rate of 13×10^-4mm³/(N·m), which was only 0.59 times of that for the mullite coating. After wear test, obvious ploughs and local spallations could be observed on the surface of mullite coating, while the surface of the Ni-P plated powder coating was smooth with less spallation. Besides, the wear forms of the two coatings were mainly plastic deformation and abrasive wear.