[15][14] According to X-ray crystallography, anhydrous AlF3 adopts the rhenium trioxide motif, featuring distorted AlF6 octahedra.

The other trihalides of aluminium in the solid state differ, AlCl3 has a layer structure and AlBr3 and AlI3, are molecular dimers.

[17][page needed] In the gas phase aluminium fluoride exists as trigonal molecules of D3h symmetry.

It is into this molten salt that aluminium oxide is dissolved and then electrolyzed to give bulk Al metal.

[12] Aluminium fluoride complexes are used to study the mechanistic aspects of phosphoryl transfer reactions in biology, which are of fundamental importance to cells, as phosphoric acid anhydrides such as adenosine triphosphate and guanosine triphosphate control most of the reactions involved in metabolism, growth and differentiation.

Like magnesium fluoride it is used as a low-index optical thin film, particularly when far UV transparency is required.

[24] Data on the potential neurotoxic effects of chronic exposure to the aluminium species existing in water are limited.