The reactions of 3-nitro-4-chlorobenzotrifluoride (1a) and 3,5-dinitro-4-chlorobenzotrifluoride (1b) with heterocycles (2–5) are described. Six S-linked and N-substituted heterocycles (6, 9–11, 13), such as 2-(2-nitro-4-trifluoromethylphenylthio) benzothiazole (9a), were prepared from the reactions of1awith benzotriazole (2). 2-mercaptobenzothiazole (5a) and 2-mercaptobenzoxazole (5b) and from the reactions of1bwith2. 1,2,4-triazole (3) and5ain DMF respectively.1areacted with 2-mercaptothiazoline (4) to give desired product 7 and bis(2-nitro-4-trifluoromethylphenyl) thioether (8), 3-(2-Benzoxazolyl)-2-benzoazolinethione (15) was obtained from the reaction of1bwith5b. The spectral data and elemental analyses were fully in accord with the proposed structures, and the possible mechanisms for these compounds and other by-products were discussed.