The material was first claimed by Ruff and Wallstein who reduced zirconium tetrachloride with aluminium to give impure samples.

[4] Subsequently, the problem with aluminium contamination was solved when it was prepared by reduction using zirconium metal:[5] When aluminium is used as the reducing agent with zirconium tetrachloride, a series of choloroaluminates are formed, for example [Zr(AlCl4)2(AlCl4)2] and Zr(AlCl4)3.

[6] Since the trihalides, such as zirconium trichloride, are comparatively nonvolatile, contamination can be avoided by using a gaseous reductant.

[2] The magnetic susceptibility of zirconium trichloride suggests metal-metal interactions of the unpaired electron on each Zr(III) center.

The magnetic moment of ZrCl3 (0.4 BM) indicates considerable overlap of metal orbitals.