In 1923, chemist Moses Gomberg proposed a production method of chlorine tetroxide.

He claimed that treating iodine and silver perchlorate in anhydrous diethyl ether produced it.

In 1968, Eachus synthesized it by exposing potassium chlorate to gamma rays at 77 K. It is a reaction intermediate of the decomposition of dichlorine heptoxide.

[citation needed] The electron affinity energy of chlorine tetroxide can be figured out using the Born–Haber cycle and the lattice energy data of perchlorates.

[4] The structure of chlorine tetroxide is uncertain; the molecular point group may be Cs, C2v, or Td.