HfCl4 can be produced by several related procedures: Hafnium and zirconium occur together in minerals such as zircon, cyrtolite and baddeleyite.

The hafnium tetrachloride remains substantially unchanged during the reduction and may be recovered readily from the zirconium subhalides.

[10] The compound hydrolyzes, evolving hydrogen chloride: Aged samples thus often are contaminated with oxychlorides, which are also colourless.

In the presence of phosphine ligands, reduction can be effected with potassium-sodium alloy:[15] The deep green dihafnium product is diamagnetic.

X-ray crystallography shows that the complex adopts an edge-shared bioctahedral structure, very similar to the Zr analogue.

Hafnium tetrachloride is the precursor to highly active catalysts for the Ziegler-Natta polymerization of alkenes, especially propylene.

[18] It was found to yield better results than other Lewis acids when used with aryl and aliphatic aldoximes, allowing specific exo-isomer formation.

[19] However, due to its relatively low volatility and corrosive byproducts (namely, HCl), HfCl4 was phased out by metal-organic precursors, such as tetrakis ethylmethylamino hafnium (TEMAH).