In this study, the potential formation of trichloronitromethane (TCNM) from model organic compounds in ammonia-containing water treated by UV/chlorine process was evaluated. Monochloramine generated from the reaction of chlorine and ammonia can be photolyzed to produce NO and reactive nitrogen species (RNS), which play important roles in the formation of TCNM during the subsequent chlorination. The results showed that increase of nitrogen to chlorine molar ratio (from 0 to 1.0) and pH (from 6.5 to 8.0) enhanced the formation of TCNM, mainly due to the increased yield of NO and RNS from the photolyzed monochloramine. The formation of TCNM was interestingly found to be linearly correlated with Hammett constants of the model precursors, which is theoretically related to the rate constants of RNS with model compounds. Enhanced formation of TCNM was also observed during the treatment of natural organic matter by UV/chlorine process in ammonia-containing water. The toxicity assessment showed that TCNM significantly increased the genotoxicity of formed DBPs. Furthermore, the electrophilic substitution reaction of NO was proved to more likely occur on the ortho and para position of phenol according to the calculation of Gaussian program, and a possible reaction pathway of phenol and NO was proposed based on the calculated results.