Among　numerous　heterometallic　chalcogenidoantimonates,　relatively　a　few　amine-directed　Ge-Sb-S　compounds　have　been　synthesized.　Presented　here　are　the　solvothermal　syntheses,　crystal　structures,　and　ion-exchange,　optical,　and　photocatalytic　properties　of　two　novel　amine-directed　Ge-Sb-S　compounds,　namely,　[CH3NH3](20)Ge10Sb28S72　center　dot　7H(2)O　(1)　and　[(CH3CH2CH2)(2)NH2](3)Ge3Sb8S15　center　dot　0.5(C2H5OH)　(2).　The　structure　of　1　features　an　unprecedented　two-dimensional　Ge-Sb-S　double-layer　composed　of　two　twofold　rotational　symmetry-related　thick　[Ge8Sb28S72](n)(28n-)　single　layers　adhered　via　vertex-sharing　[GeS4]　tetrahedra.　Compound　2　features　a　unique　[Ge3Sb5S15](n)(3n-)　slab　perforated　with　large　elliptic-like　windows.　Remarkably,　compound　1　exhibited　excellent　Cs+　ion-exchange　property　despite　the　presence　of　excess　competitive　cations,　such　as　Na+,　K+,　Mg2+,　and　Ca2+　ions.　In　addition,　compound　1　displayed　visible-light-driven　photo　catalytic　activity　for　degradation　of　rhodamine　B.