A decanuclear gold(I)-sulfido complex, [(L-H)(4) Au10S4]Cl-2 (L-H-Au10S4 -Cl, where L-H = 4,5-bis-(diphenylphosphanyl)-2H-1,2,3-triazole), assembled from the reaction of H2S with the chlorogold(I) precursor obtained from the click reaction of [dppa(AuCl)(2)] (where dppa = 1,2-bis-(diphenylphosphino)acetylene) with NaN3, is shown to display a bright dual green and red emission in the solid state. Single crystal X-ray diffraction (SCXRD) studies indicate a gold(I) cluster-based framework assembled through intermolecular halogen center dot center dot center dot hydrogen bonds as well as other weak interactions. The framework of L-H - Au10S4-Cl is found to display high stability toward solvent molecules, with capability to encapsulate solvent molecules, such as benzene and cyclohexane, inside the crystal lattice voids via a single-crystal-to-single-crystal (SCSC) transformation. With different degrees of influence on the dual green and red emission, crystalline solids of L-H-Au10S4-Cl exhibit remarkable solvatochromic luminescence in the presence of benzene and cyclohexane. Notably, due to the size confinement of the lattice cavities, the L-H-Au10S4-Cl solids exhibit a high selectivity (>95%) toward benzene in a mixture of equimolar concentration of benzene and cyclohexane. This work has demonstrated the promising capability of gold(I)-sulfido cluster frameworks to serve as luminescent functional materials for the separation of benzene and cyclohexane.