New coatings resistant to corrosion in high-temperature molten zinc aluminum were prepared by supersonic flame spraying of various composite powders. These composite powders were prepared by mixing, granulation, and heat treatment of various proportions of Mo–B4C powder and WC and Co powder. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF–STEM), energy dispersive X-ray spectroscopy (EDS), and mechanical analysis were used to study the effects of Mo–B4C on the microstructure, phase, porosity, bonding strength, and elastic modulus of the composite powder and coating. Results show that the addition of an appropriate quantity of Mo–B4C reacts with Co to form ternary borides CoMo2B2 and CoMoB. Ternary boride forms a perfect continuous interface, improving the mechanical properties and corrosion resistance property of the coating. When the amount of Mo–B4C added was 35.2%, the mechanical properties of the prepared coating reached optimal values: minimum porosity of 0.31 ± 0.15%, coating bonding strength of 77.81 ± 1.77 MPa, nanoindentation hardness of 20.12 ± 1.85 GPa, Young’s modulus of 281.52 ± 30.22 GPa, and fracture toughness of 6.38 ± 0.45 MPa·m1/2.