Fluorine-19 NMR spectroscopy, even at temperatures as low as −100 °C, fails to distinguish the axial from the equatorial fluorine environments.

The apparent equivalency arises from the low barrier for pseudorotation via the Berry mechanism, by which the axial and equatorial fluorine atoms rapidly exchange positions.

Electron diffraction and X-ray crystallography do not detect this effect as the solid state structures are, relative to a molecule in solution, static and can not undergo the necessary changes in atomic position.

With primary and secondary amines, the adducts convert readily to dimeric amido-bridged derivatives with the formula [PF4(NR2)]2.

It is often used in lithium-ion batteries, where besides providing good ionic conductivity for the liquid electrolyte, it also passivates positive aluminium current collector.