Treatment of keto‐functionalized organotin sulfide [(R1Sn)4S6] {A; R1 = C(Me)2CH2C(Me)O} or its derivative [(RfC1Sn)4S6] {B, RfC1 = fC[C(O)NH–N=(Me)CCH2(Me)2C]2} with acids or bases leads to a variety of novel organo‐functionalized tin sulfide/oxide cages. In addition to rearrangements of the inorganic core, the compounds comprise different organic decorations with ligands R2 = C(Me)2CH2C(Me)=N–NH2, RfC2 = [C(Me)2CH2C(Me)=N–NHC(O)]fC[C(–O)=N–N=C(Me)CH2(Me)2C], RfC3 = fC[C(–O)=N–N=C(Me)CH2(Me)2C]2, RfC4 = [C(Me)2CH2C(Me)=N–NHC(O)]fC[C(O)NH–NH2], and RfCO = [fC(COO)2]2–. We show how the reaction conditions influence the course of the reactions and hence the nature of the products, among them a series of mixed‐valent complexes based on [SnII(SnIV)2S4] defect‐heterocubane units.