In the gas phase and in the crystal, the species adopts a pyramidal structure, in accord with VSEPR theory.

or by dissolving bismuth metal in aqua regia, evaporating the mixture to give BiCl3·2H2O, which can be distilled to form the anhydrous trichloride.

Also, the compound can be prepared by dissolving bismuth in concentrated nitric acid and then adding solid sodium chloride into this solution.

In contrast to the usual expectation by consistency with periodic trends, BiCl3 is a Lewis acid, forming a variety of chloro complexes such as [BiCl6]3− that strongly violates the octet rule.

Furthermore, the octahedral structure of this coordination complex does not follow the predictions of VSEPR theory, since the lone pair on bismuth is unexpectedly stereochemically inactive.