Molybdenum boride is an ideal hard and wear-resistant material. In this study, a new method is proposed for preparing molybdenum boride, by which Mo first reacts with B4C to generate the mixture of molybdenum boride and C, and then the product is decarburized by molten Ca to generate CaC2. Pure molybdenum boride could be obtained after acid leaching to remove the by-product CaC2. According to the experimental and thermodynamic calculation results, it is concluded that the single-phase MoB could be successfully prepared, while Mo2B, Mo2B5, and MoB4 could not be synthesized by this method. Moreover, it was found that the particle size of finally prepared MoB is determined by particle size of raw Mo powder. The residual carbon content of the product could be decreased to 0.10 wt% after first reaction at 1673 K for 6 hours and then decarburization reaction at 1673 K for 6 hours.