Trifluoromethyl trifluoromethanesulfonate has proved to be an excellent reservoir of difluorophosgene and a promising click ligation for amines in the preparation of urea derivatives, heterocycles, and carbamoyl fluorides under metal‐ and additive‐free conditions. The reactions are rapid, efficient, selective, and versatile, and can be performed in benign solvents, giving products in excellent yields with minimal efforts for purification. The characteristics of the reactions meet the requirements of a click reaction. The use of trifluoromethyl trifluoromethanesulfonate as a click reagent is advantageous over other “CO” sources (e.g., TsOCF3, PhCO2CF3, CsOCF3, AgOCF3, and triphosgene) because this reagent is readily accessible; easy to scale up; and highly reactive, even under metal‐ and additive‐free conditions. It is anticipated that CF3SO3CF3 will be increasingly as important as SO2F2 as a click agent in future drug design and development. Back to basics: Trifluoromethyl trifluoromethanesulfonate is a promising click reagent for amines in the preparation of urea derivatives, heterocycles, and carbamoyl fluorides under metal‐ and additive‐free conditions (see scheme). The click reactions are rapid, efficient, and selective, and simply carried out in benign solvents to afford products with minimal efforts for purification.