Treatment of chloropermethylcyclohexasilanes Si6Me12− n Cl n (n= 1− 3) with NH3 or NaNH2, respectively, affords previously unknown aminocyclohexasilanes, which are surprisingly stable toward self-condensation in the pure state. Under slightly acidic conditions polysilazanes with linear, branched, or cagelike structures still containing intact cyclohexasilanyl moieties are formed by loss of NH3.