A fluorine-19 nuclear magnetic resonance study was made of the polycrystalline solid electrolytes MThF//6 (M equals Ca, Cd, Sr, Pb, Ba) and Pb//0//. //1Bi//0//. //9F//2//. //9. It was found that the polarizability and charge inhomogeneity in the cation sublattice of these tisonite-like fluorides affect the diffusion of properties of the fluorine ions in the low-temperature range, but promote an increase in their mobility in comparison with isostructural rare-earth trifluorides in the high-temperature range. Moreover, a decrease in the dynamic inhomogeneity in the anion subsystem is observed.