Self‐assembly with non‐covalent interactions (NCIs) is a ubiquitous phenomenon observed in biology and materials chemistry, while its application in synthetic chemistry is still in its infancy. Herein, a self‐assembly condensation method from sulfonamides and imides is reported, leading to the formation of N‐acyl‐N’‐sulfonyl amidines. DFT calculations and NMR investigations suggest that the process is facilitated by cooperative assisted NCIs, including hydrogen bonding and Lewis pairs. Moreover, this methodology can be applied in the late‐stage derivatization of bioactive and complex sulfonamides, offering a potential avenue for the discovery of drug molecules. Extension of this methodology to the condensation of various sulfonamides and amides has also been successfully achieved.