The salt is a hygroscopic bright yellow crystalline solid at room temperature.

Above 200 °C, it tends to decompose into polonium dichloride and excess chlorine, similar to selenium tetrachloride and tellurium tetrachloride.

Polonium tetrachloride is bright yellow at room temperature.

Its vapours are purple-brown until 500 °C, when they turn blue-green.

[1] Polonium tetrachloride may be prepared by: Polonium tetrachloride forms a complex with two moles of tributyl phosphate.