The metal ceramic powder with a particle size of 15-45 µm and suitable for thermal spraying is prepared through a combination of mechanical ball milling, spray granulation, and vacuum sintering. The metal ceramic powder is sprayed on a surface of a steel substrate adopting the high velocity oxygen fuel (HVOF) technology with oxygen-propane as fuel and taking oxygen as a combustion improver, propane as fuel, nitrogen as powder feeding carrier gas, and air as a cooling medium to prepare and form the NiCrBSi—ZrB2 composite coating. The present disclosure solves the problem that ZrB2 ceramic is difficult to compact during sintering and improves powder bonding strength and fluidity. The preparation method is simple, has advantages of high coating deposition efficiency and convenient equipment operation, and is cost-effective. The preparation method can improve thermal corrosion resistance and high-temperature wear resistance of a surface of boiler, and prolonging lifetime of the boiler.