[NEt3Me][O3] was obtained for the first time by an ion exchange reaction in liquid ammonia. It was thoroughly characterized by X‐Ray diffraction [P21; a=598.51(4) pm, b=1032.03(7) pm, c=723.83(6) pm, β=92.677(3)°, R=0.0384, 15070 reflections] applying non‐spherical and spherical atomic form factors for the refinements. In contrast to previous reported ozonides, [NEt3Me][O3] is the first to adopt the tungsten carbide (WC) motif of cation/ anion arragemnent and shows an untypical hydrogen bond between the central oxygen atom of the ozonide and the cation. Additionally, IR spectroscopy as well as quantum‐chemical calculations were applied to further characterize the compound. The obtained ozonide showed high solubility in ammonia as well as acetonitrile and good properties as a synthon in ozonide chemistry.
