Abstract The reaction of SbI3 with Me4NI, Me3SI. and Me3NCH2PhI in acetonitrile (molar ratios 2:1) yields (Me4N)4Sb8I28 (I), (Me3S)4Sb8I28 (2), and (Me3NCH2Ph)Sb2I7 (3), respectively. The structures of 1-3 were determined from single crystal X-ray diffraction data. 1-3 crystallize in the monoclinic space group P21/n. 2: a = 1434.2(3). b = 1484.1(4). c = 2102.6(4) pm, β = 105.4(1)°, Z = 2. I: a = 1441.7(1). b = 1545.1(1). c = 2117.3(1) pm. β = 106.4(1)°, Z = 2. 3: a = 1004.4(1). b = 1378.8(1). c = 1899.3(2) pm. β = 94.2(1)°. Z = 4. The structures of I and 2 are very similar and consist of isolated cations and anions. The Sb8I28 4- ions of 1 and 2 and the anion of the same stoichiometry of (Ph4P)4Sb8I28 exhibit different structures with a nearly identical Sb4I16 core. The anions of 3 are built up of polymeric cfiains.