The halosilicates(II) [nBu4N]2[Si6Br12·2Br] and [nBu4P]2[Si6I12·2I] were prepared by mere addition of the appropriate halide salt to the corresponding disilane Si2X6 (X = Br, I). In the first case, the Br3Si‐substituted derivative [nBu4N]2[Si7Br14·2Br] formed as a second product. We have been able to obtain single crystals of [Ph4P]2[Si7Br14·2Br] by switching the Br– salt from [nBu4N]Br to [Ph4P]Br. All three compounds, [nBu4N]2[Si6Br12·2Br] (monoclinic, P21/c), [nBu4P]2[Si6I12·2I] (triclinic, P1), and [Ph4P]2[Si7Br14·2Br] (triclinic, P1) were structurally characterized by X‐ray crystallography and found to form “inverse sandwich complexes”, in which two X– ions are located above and below a planarized Si6 ring. The free periodated cyclohexasilane Si6I12 is accessible from [nBu4N]2[Si6Cl12·2Cl] and BI3 (1:5 molar ratio; CH2Cl2) via a decomplexation/halide‐exchange cascade. Si6I12 (monoclinic, C2/c) adopts a puckered chair conformation in the solid state. The cyclopentasilane diadduct [nBu4P]2[Si5Cl10·2Cl] forms at –78 °C from Si5Cl10 and 2 equiv. of [nBu4P]Cl in CH2Cl2. An X‐ray analysis of [nBu4P]2[Si5Cl10·2Cl]·2CH2Cl2 (monoclinic, C2/c) again revealed the structure of an “inverse sandwich complex”. Crystalline [nBu4P]2[Si5Cl10·2Cl]·2CH2Cl2 is stable at room temperature. However, in CH2Cl2 solution the compound quantitatively undergoes ring‐expansion reactions to furnish cyclohexasilane derivatives. This behavior is in striking contrast to that of [nBu4N]2[Si6Cl12·2Cl], which persists at room temperature both in solution and the solid state. Competition experiments revealed free Si5Cl10 and Si6Cl12 to have comparable Cl– affinities, even though the distance between the two apical Cl– ions in [Si5Cl10·2Cl]2– (4.292 Å) is larger by 0.456 Å than that in [Si6Cl12·2Cl]2– (3.836 Å).