Many municipalities in Canada and all over the world use chloramination for drinking water secondary disinfection to avoid DBPs formation from conventional chlorination. However, the long-lasting monochloramine (NH2Cl) disinfectant can pose a significant risk to aquatic life through its introduction into municipal storm sewer systems and thus fresh water sources by residential, commercial, and industrial water uses. To establish general total active chlorine (TAC) concentrations in discharges from storm sewers, the TAC concentration was measured in stormwater samples in Edmonton, Alberta, Canada, during the summers of 2015 and 2016 under both dry and wet weather conditions. The field-sampling results showed TAC concentration variations from 0.02 to 0.77 mg/L in summer 2015, which exceeds the discharge effluent limit of 0.02 mg/L. As compared to 2015, the TAC concentrations were significantly lower during the summer 2016 (0–0.24 mg/L), for which it is believed that the higher precipitation during summer 2016 reduced outdoor tap water uses. Since many other cities also use chloramines as disinfectants for drinking water disinfection, the TAC analysis from Edmonton may prove useful for other regions as well. Other physicochemical and biological characteristics of stormwater and storm sewer biofilm samples were also analyzed, and no significant difference was found during these two years. Higher density of AOB and NOB detected in the storm sewer biofilm of residential areas – as compared with other areas – generally correlated to high concentrations of ammonium and nitrite in this region in both of the two years, and they may have contributed to the TAC decay in the storm sewers. The NH2Cl decay laboratory experiments illustrate that dissolved organic carbon (DOC) concentration is the dominant factor in determining the NH2Cl decay rate in stormwater samples. The high DOC concentrations detected from a downstream industrial sampling location may contribute to a high stormwater NH2Cl decay rate in this area.