The combined application of chlorination and UV irradiation has the potential to yield important benefits in water treatment. However, much of the fundamental chemistry that governs the behavior of UV/chlorine systems have not been well defined. Cyano-containing pesticides (CNPs) are widely used in agriculture and inevitably enter surface waters and other aquatic environments. In this study, twenty CNPs and their intermediates were investigated to evaluate the formation of disinfection byproducts under chlorination and UV/chlorine systems. It was found that UV/chlorine can significantly enhance the generation of cyanogen chloride (CNCl) and dichloroacetonitrile (DCAN) compared to chlorination alone. The CNCl and DCAN concentrations increased from an average of 0.13 and 0.12 μM during the chlorination alone to 0.85 and 0.41 μM, respectively, when UV254 light was introduced. The maximum yields of CNCl and DCAN could reach 31.8 % and 7.7 %, respectively. Both the photo-induced •OH and •Cl played a key role in the generation of CNCl and DCAN. Additionally, higher yields of total CNX were observed in the UV/chlorine system in the presence of bromide. Similar results were obtained in the treatment of actual water samples, in which the concentrations of CNCl and DCAN increased by orders of magnitude under UV/chlorine treatment compared to the chlorination alone. The results showed that the cyano group of organic pollutants has a higher potential to be directly converted to toxic CNCl and DCAN under UV/chlorine treatment. The inclusion of this basic chemistry will deepen our understanding of UV/chorine water treatment technologies.