The anhydrous form is produced from hydrogen fluoride and chromic chloride:

Chromium(III) chloride, also known as chromic chloride or chromium trichloride.

Chromium pentafluoride is one of the products of the action of fluorine on a mixture of potassium and chromic chlorides.

• Chromium (III)/Chromic chloride hexahydrate (O'Neil et al.

In their original 1977 publication, Tamejiro Hiyama and Hitosi Nozaki reported on a chromium(II) salt solution prepared by reduction of chromic chloride by lithium aluminium hydride to which was added benzaldehyde and allyl chloride: