A mild and efficient approach is described for generating substitution products of electron‐deficient benzenesulfonyl chlorides via intermolecular ipso aromatic nucleophilic substitution reaction. Various amines and thiols effectively undergo a transition‐metal‐free coupling process, leading to diaryl or arylalkyl amines and thioethers with the formation of C─N and C─S bonds. The regioselective attack of N‐nucleophiles produces sulfonamides in the absence of a base. This reaction generates the Smiles rearrangement products. However, a series of mechanistic investigations point toward the intermolecular pathway in contrast to the intramolecular ipso substitution, known as Smiles rearrangement.