This white solid, discovered in 1799 by Peder Christian Abildgaard (1740–1801),[4][5] occurs naturally as the mineral cryolite and is used extensively in the industrial production of aluminium.

One route entails combining sodium aluminate and hydrofluoric acid:[2] Other routes include:[6] Often the hexafluoroaluminic acid, which is recovered from phosphate mining, is the precursor in a two-step process beginning with neutralization with ammonia to give ammonium hexafluoroaluminate: The mineral form of sodium hexafluoroaluminate, which is called cryolite, was mined at Ivigtût on the west coast of Greenland until the deposit was depleted in 1987.

The dominant application of synthetic cryolite is as a solvent (or flux) for electrolysis of aluminium oxides such as bauxite.

The conversion of aluminium oxides into metallic aluminium requires that the metal ions be dissolved so that they can accept the electrons provided in the electrolysis cell.

Unlike typical solutions, this one requires temperatures approaching 1000 °C to melt.