These hygroscopic salts are common precursors to other vanadium(III) complexes and is used as a mild reducing agent.

[6] VCl3 has the common layered BiI3 structure, a motif that features hexagonally closest-packed chloride framework with vanadium ions occupying the octahedral holes.

[10][11] The hexahydrate phase loses two water of crystallization to form the tetrahydrate if heated to 90 °C in a stream of hydrogen chloride gas.

[18] Vanadium trichloride catalyses the pinacol coupling reaction of benzaldehyde (PhCHO) to 1,2-diphenyl-1,2-ethanediol by various reducing metals such as zinc:[19] VCl3 forms colorful adducts and derivatives with a broad scale of ligands.

In other words, two of the water molecules are not bound to the vanadium, whose structure resembles the corresponding Fe(III) derivative.

When treated with KCN, VCl3 converts to [V(CN)7]4− (early metals commonly adopt coordination numbers greater than 6 with compact ligands).

Vanadium(III) chloride is able to form complexes with other adducts, such as pyridine or triphenylphosphine oxide.