A green process was developed for the preparation of 2-bromothiophene by using thiophene, a by-product of crude benzene extraction, as reactant, hydrogen peroxide as oxidant and bromine-containing inorganic waste as bromine source, and the selective electrophilic substitution reaction mechanism was analyzed. When the reaction temperature was-10 ℃-10 ℃, and the equimolar ratio was applied, the yield of the target product 2-bromothiophene reached about 95%, and the atomic utilization reached 100% through the recycling process. Moreover, the problem of uneven mixing of materials due to heterogeneous reaction in the process of industrialization was solved. Compared with other processes using cosolvent or bromination reagent, the process avoided the use of solvents and uses bromine-containing inorganic wastes as bromine sources. In the process of industrialization, the recycling of by-product magnesium chloride could greatly reduce the emission of three wastes and be promising to product 2-bromothiophene at hundreds of tons.