Anhydrous chromium(III) chloride adopts the YCl3 structure,[6] with Cr3+ occupying one third of the octahedral interstices in alternating layers of a pseudo-cubic close packed lattice of Cl− ions.

For this reason, crystals of CrCl3 cleave easily along the planes between layers, which results in the flaky (micaceous) appearance of samples of chromium(III) chloride.

[9] The hydrated chromium(III) chlorides display the somewhat unusual property of existing in a number of distinct chemical forms (isomers), which differ in terms of the number of chloride anions that are coordinated to Cr(III) and the water of crystallization.

This chromium(II) compound undergoes substitution easily, and it can exchange electrons with CrCl3 via a chloride bridge, allowing all of the CrCl3 to react quickly.

Similarly, ligand substitution reactions of solutions of [CrCl2(H2O)4]+ are accelerated by chromium(II) catalysts.

The hexahydrate can also be dehydrated with thionyl chloride:[13] CrCl3 is a Lewis acid, classified as "hard" according to the Hard-Soft Acid-Base theory.