The invention relates to the technical field of preparation of o-dibromobenzene, and particularly relates to a method of synthesizing o-dibromobenzene by diazotization in one step at high temperature. The method comprises the following steps: sequentially adding hydrobromic acid, cuprous oxide and bromaniline into a reactor with a stirrer, a condenser and a thermometer; heating to over 80 DEG C; maintaining the temperature within 80-100 DEG C; dropping aqueous solution of sodium nitrite under liquid level; after dropping, distilling with steam to obtain the product, and separating out the oil layer; washing once by thermonatrite; after washing once, distilling under reduced pressure to obtain a product. According to the preparation method of o-dibromobenzene provided by the invention, diazotization and decomposition reaction are carried out by using a one-step method, so that the energy consumption and investment on freezing equipment are greatly reduced, and the product is stable in yield, and yield fluctuation caused by refrigeration of a two-step method is avoided. The continuous production capacity is greatly improved, the quality of the product is consistent with that of the two-step method, the yield is slightly higher, the preparation process is simple, convenient and feasible, the product is good in quality, and the technical demand is low, so that the method is a method suitable for industrialized production.