Chlorosulfonamide reacts in the superacidic solutions HF/GeF4 and HF/AsF5 under the formation of ([ClSO2NH3]+)2[GeF6]2– and [ClSO2NH3]+[AsF6]–, respectively. The chlorosulfonammonium salts were characterized by X‐ray single crystal structure analysis as well as vibrational spectroscopy and discussed together with quantum chemical calculations. ([ClSO2NH3]+)2[GeF6]2– crystallizes in the triclinic space group P1 with one formula unit in the unit cell. [ClSO2NH3]+[AsF6]– crystallizes in the monoclinic space group P21/n with four formula units in the unit cell. Dependent on the counterion, [AsF6]– or [GeF6]2–, considerable structural differences of the [ClSO2NH3]+ cation are observed. Furthermore, the hitherto unknown X‐ray single crystal structure of chlorosulfonamide is determined in the course of this study. Chlorosulfonamide crystallizes in the orthorhombic space group Pmc2 with four formula units per unit cell.