Many metal clusters are intrinsically chiral but are often synthesized as a racemic mixture. By taking chiral Ag(SPh(CF))(PPh)(DMF) () clusters with bulky thiolate ligands as an example, we demonstrate herein an interesting assembly disassembly (ASDS) strategy to obtain the corresponding, optically pure crystals of both homochiral enantiomers, and . The ASDS strategy makes use of two bidentate linkers with different chiral configurations, namely, (1,2,,)-,-bis(pyridin-3-ylmethylene)cyclohexane-1,2-diamine () and the corresponding chiral analogue . For comparison, we also use the racemic mixture of equimolar of and (). Three three-dimensional (3D) Ag-based metal-organic frameworks (MOFs) were characterized by X-ray crystallography to be [Ag(SPh(CF))(PPh)(LR)] (), [Ag(SPh(CF))(PPh)(LS)] (), and [Ag(SPh(CF))(PPh)(LRS)] (), respectively. As expected, the building blocks in or are homochiral or , respectively. In contrast, is achiral and crystallizes with a diamond-like structure containing alternate and clusters. During the assembly process, the racemic clusters were converted to homochiral building blocks, namely, for and for . Subsequently, the chiral linkers were removed from the crystals of and via hydrolysis with water, and from the disassembled solid material and , optically pure enantiomers and were obtained. It is hoped that this simple assembly strategy can be used to construct cluster-based chiral assemblage materials and that the subsequent disassembly protocol can be used to obtain optically pure chiral cluster molecules from as-prepared racemic mixtures.