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.