Coagulation is a widespread method of drinking water treatment. Coagulation can mitigate the formation of disinfection by-products (DBPs) through removing their precursors. Here we report that the amide-based organic polymer coagulants polyacrylamide (PAM) and its monomer acrylamide (AM) can serve as a source of HAcAm and other DBPs including trihalomethanes (THMs) and haloacetonitriles (HANs) during chlor(am)ination. The impact of the key experimental parameters, including reaction time, Cl2 or NH2Cl dose, pH and initial bromide concentration on the formation of DBPs was investigated. Furthermore, the major reaction pathways for AM transformation and DBP formation during chlor(am)ination are proposed and include N-chlorination, addition, and substitution. Jar tests demonstrated that coagulation by alum coupled with PAM achieved greatest removal of DOC and UV254, compared with alum and PAM alone. Treatment with PAM didn’t significantly promote the formation of THMs and HANs during post-chlorination, indicating that the PAM residual hardly contributes to THM and HAN formation. However, coagulation by applying alum salt and PAM increased total HAcAm concentrations by 2.2–3.1 μg/L at the higher PAM dose (2.0 mg/L), compared with alum alone. Therefore, the contribution of PAM to the formation of HAcAm cannot be ignored. The results highlight that the generation of secondary pollutants from the amide-based engineered organic polymer coagulants in drinking water should be considered; that is, they can adversely affect water quality because of their ability to enhance DBPs generated during downstream disinfection. Accordingly, the understanding of the stability and reactivity of PAM in the presence of disinfectants could help to better evaluate their contribution to the formation of HAcAms, THMs, and HANs, which has important implications for their environmental fate, transport, and responsible applications.