Abstract The crystal and molecular structures of triethylammonium tetrachloroantimonate(III) (1) and tris[methylammonium] hexachloroantimonate(III) (2) were determined by X-ray analysis. In compound 1, SbCl3 molecules are bridged by Cl ions to form chains. The coordination of Sb by Cl atoms yields a distorted tetragonal-pyramidal structure. In compound 2 there are chains of SbCL4 - ions, again through bridging by Cl ions. One Cl ion has no contacts to Sb. The cations of 1 and 2 form hydrogen bonds with the anionic components.