Transition metal borides have been used widely as multi-functional hard materials in industrial production. However, the crystal structure of some materials is still controversial. These materials can’t be distinguished by conventional test methods (XRD, EDS, etc.). The distinguished test method are complex and expensive. But, synthesizing pure phase materials is also a challenge, which  brings more trouble to the determination of the crystal structure of the sample. In this paper, WB₂ with controversial crystal structure was synthesized by high temperature and high pressure method. The crystal structure was determined to be WB₂ instead of W₂B₅ by the combination of theory and experiment. This method is important to determine the crystal structure of controversial crystal structure materials.