The reactions of 1,3‐dinitro‐2‐chloro‐5‐trifluorotoluene (DNCTT) (1) and its bridged compounds with bidentate nucleophiles have been investigated. Primary or secondary diamines and diethylene glycol react with 1 and its bridged derivatives by replacing the substituent group para to CF3, whereas ethanedithiol reacts either by replacing the substituent group para to CF3 or by displacing both groups and a nitro group. The results have been rationalized in terms of electronic effects and nucleophilicity of the nucleophiles.