An eco‐friendly and efficient method was developed for synthesizing a novel class of aliphatic sulfonyl fluorides in a catalyst‐free one‐pot reaction. The new approach offers a streamlined synthesis for N‐(Substituted)‐2‐(fluorosulfonyl) ethyl carbamodithioates by combining amines, carbon disulfide, with ethenesulfonyl fluoride. The synthesized compounds were obtained in good yields under mild conditions, making this reaction a valuable tool for exploring new chemical transformations.