Attempts to prepare Cs[MVIF7] and Cs2[MVIF8] salts by photochemical reactions between CsF, noble metal M (M = Ru, Rh, Os, Ir, Pt) and UV-irradiated F2 in anhydrous HF failed. The main products were Cs[MVF6] salts. The formation of MF6 (M = Rh, Os, Ir) was also observed. The reaction between PtF6 and a solution of CsF in anhydrous HF resulted in the formation of CsPtF6 and the release of elemental F2. The crystal structures of the Cs[MVF6] salts (M = Ru, Rh, Os, Ir, Pt) were determined on single crystals. They are isotypic and crystallize in the trigonal space group R ̅3 (No. 148), belonging to the KAsF6 (KOsF6) family of crystal structures. The Raman spectra of Cs[MF6] salts (M = Ru, Rh, Os, Ir, Pt) are also described.