Recent epidemiological studies reported that brominated DBPs may be more carcinogenic than their chlorinated analogs. Thus, this research was designed to investigate the role of bromide ion in the formation and speciation of disinfection by-products (DBPs) during chlorination of Buyukcekmece Lake Water (BLW) in Istanbul. Chlorination of BLW samples was carried out at pH 7.0 with 5 and 12 mg/l chlorine dosages. For each chlorine dosage, six bromide concentrations ranging from 0.05 to 4.0 mg/l were added to form a 2 × 6 experimental matrix. In general, increasing bromide concentration gradually shifted trihalomethanes (THMs) and haloacetic acids (HAAs) speciation from chlorinated species to the mixed bromochloro species during chlorination. The halogen substitution ability of HOBr and HOCl during the formation of THMs and HAAs can be estimated through the use of probability theory. It was concluded that, in both halogen substitution for THM and dihalogenated HAA formation, HOBr was found to be 20 times more reactive than HOCl.