A decanuclear gold(I)–sulfido complex, [(L^H)₄Au₁₀S₄]Cl₂ (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···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.