While systems K 3 TaF 8 and K 3 ZrF 7 were prepared by modified molten salt method modified wet pathway was used for reproducible preparation of Na 7 Zr 6 F 31 . Its congruently melting character was demonstrated on simultaneous TG/DSC measurements and XRD patterns. X-ray photoelectron spectroscopy was applied for identification of differently bonded fluorine atoms in series of compounds NaF, K 2 TaF 7 , K 3 TaF 8 , K 2 ZrF 6 , Na 7 Zr 6 F 31 and K 3 ZrF 7 . Three different types of fluorine atoms were described qualitatively and quantitatively. Uncoordinated fluorine atoms (F − ) provide signals at lowest binding energies, followed by signals from terminally coordinated fluorine atoms (M–F) and then bridging fluorine atoms (M–F–M) at highest energy. Based on XPS F 1s signals assigned to fluorine atoms in compounds with correctly determined structure it was suggested that fluorine atoms in K 3 ZrF 7 have partially bridging character.