The phase transitions of two ternary fluorides have been reinvestigated by
thermal and X-ray diffraction analyses. Four phase transitions have been de
tected at T-1 =483 +/- 5 K, T-2= 548 +/- 5 K, T-3 = 765 +/- 5 K and T-4= 86
7 +/- 5 K for Li3AlF6. Only two transformations occurred at T-1 = 550 +/- 5
K and T-2 = 660 +/- 10 K for Li3CrF6 Dielectric and optical measurements p
erformed respectively on ceramics and single crystals revealed a ferroelect
ric behaviour coupling partially with ferroelastic coupling for the two inv
estigated fluorides.