A mild and regioselective bromination of phenols with the cheap and easily-available HBr is developed. By replacing the common used dimethyl sulfoxide (DMSO) with sulfoxides bearing sterically hindered substituents, the desired brominated phenols could be obtained in moderate to high yields with up to 99/1 regioselectivity. This method could be easily scaled up to 50 mmol scale and has the potential to isolate the desired product by simple extraction and recrystallization, showing great practicality of this new method.