A route to salts of the [ClOF2]+ cation is described that does not require the parent fluoride ClOF3 as a starting material. These can be obtained when either metals such as Cr, Rh, Pd and Au, halides such as PtCl2, SnF2 and PbF4, or oxides such as B2O3, OsO4, GeO2, SnO and Sb2O4 are reacted with ClF3 and additional O2, where necessary, under UV irradiation. Cr, Rh, Pd, PtCl2, GeO2, and SnO formed salts with the respective hexafluoridometallate(IV) anion with the composition [ClOF2]2[MF6]. They crystallize in two distinct structure types in either the monoclinic crystal system (M=Cr, Rh, Ge) or the orthorhombic one (M=Pd, Pt, Sn). The fluorides SnF2 and PbF4 were converted to the monoclinic salts [ClOF2]MF5, and B2O3 formed orthorhombic [ClOF2][BF4]. The triclinic compound ([ClOF2][OsO3F3])2⋅OsF6 was obtained from OsO4 and contains a neutral co‐crystallized OsF6 molecule. A monoclinic double salt with the composition [ClOF2]2[AuF4][SbF6] was obtained by reacting a mixture of Sb2O4 and Au. The compounds were investigated by single crystal X‐ray diffraction and IR and Raman spectroscopy. Quantum‐chemical calculations for the solid‐state allowed for the band assignments of the vibrational spectra.