Extended information is provided about ¹⁹F MAS NMR and XPS spectroscopic data on 11 ternary fluorido-zirconates (Li₂ZrF₆, Rb₂ZrF₆, Cs₂ZrF₆, Na₃ZrF₇, (NH₄)₃ZrF₇, K₃ZrF₇, Li₄ZrF₈, K₂ZrF₆, Na₅Zr₂F₁₃, Na₇Zr₆F₃₁, and (NH₄)₂ZrF₆), which display different coordination numbers of the zirconium atom as well as different modes of fluorine atom bonding. XPS data show that binding energies on fluorine 1s electrons are sensitive to its coordination properties (ionic, terminal or bridging coordination mode) while the binding energies of zirconium orbitals are not sensitive to its coordination properties (six-, seven- or eightfold coordination). ¹⁹F chemical shifts correlate with the ionic radii of counter cations along the series Li₂ZrF₆, Rb₂ZrF₆, Cs₂ZrF₆ and K₃ZrF₇, (NH₄)₃ZrF₇ and Na₃ZrF₇. This reflects the polarizability properties and shielding potential of the cations surrounding the fluorine atoms. Additionally, calculations of NMR parameters for the compounds were also carried out using the CASTEP DFT code. The correlation between the experimental isotropic chemical shifts and calculated isotropic chemical shieldings established for the studied compounds allows us to predict the ¹⁹F NMR spectrum of crystalline compounds with good accuracy. A unique technique of low temperature ¹⁹F MAS NMR experiments combined with CASTEP calculation on (NH₄)₂ZrF₆ enabled the assignment of all 12 crystallographically non-equivalent fluorine atoms to NMR signals.