Abstract Aryl halides containing electron‐withdrawing substituent(s) at ortho and para position undergoes aromatic nucleophilic substitution reaction with sulfur nucleophile present in dithiocarbamate anions at room temperature. In the present study, several cyclic and acyclic secondary amines reacted in situ with carbon disulfide to form dithiocarbamate anions, which then react with different haloarenes resulting in the formation of aryldithiocarbamates. A series of aryldithiocarbamates are obtained in high yields by this procedure.