(LiL)(2)Li3SbS3 was prepared by solid-state reaction of stoichiometric amounts of Lil, Li, Sb, and S in the ratio 2 : 3 : I : 3. The product is air and moisture sensitive. The crystal structure was determined from single crystals at room temperature. Colourless to pale yellow (Lil)(2)Li3SbS3 crystallizes in the orthorhombic system, space group Pnnm (no. 58) with a = 10.436(l) Angstrom, b = 13.509(l) Angstrom, c = 7.530(l) Angstrom. V = 1061.6(l) Angstrom(3), and Z = 4 (data at 20 degreesC). The crystal structure of (Lil)(2)Li3SbS3 is closely related to that of (CuI)(2)Cu3SbS3 and (AgI)(2)Ag3SbS3, at least for the positions of 1, Sb, and S. Thus, iodine forms an eutactic arrangement which resembles the structure of hexagonal diamond. [SbS3](3-) units are embedded in this framework in a way that the sulphur atoms of two adjacent trigonal pyramids form distorted octahedral voids. The lithium ions are tetrahedrally coordinated and fully ordered within the anionic framework. The three-dimensional connectivities in (Lil)(2)Li3SbS3 are significantly different from the homologous copper and silver compound due to the bonding necessities of Li and slightly different radii of the monovalent cations. Thus, a novel three-dimensional network of edge sharing tetrahedra is observed in (Lil)(2)Li3SbS3. It exhibits strands of eight-membered rings of edge sharing tetrahedra which are linked by common vertices and cross linked by double tetrahedra.