Polonium dichloride appears to crystallise with an orthorhombic unit cell in either the P222, Pmm2 or Pmmm space group, although this is likely a pseudo-cell.

Alternatively, the true space group may be monoclinic or triclinic, with one or more cell angles close to 90°.

[1] Methods for dehalogenating PoCl4 include thermal decomposition at 300 °C, reduction of cold, slightly moist PoCl4 by sulfur dioxide; and heating PoCl4 in a stream of carbon monoxide or hydrogen sulfide at 150 °C.

[2] PoCl2 dissolves in dilute hydrochloric acid to give a pink solution, which autoxidises to Po(IV).

With dilute nitric acid, PoCl2 forms a dark red solution followed by a flaky white precipitate of unknown composition.