Compound [Ag₃₁S₃(S^tBu)₁₇(CF₃COO)₇(CO₃)_0.5(CF₃COOH)_0.5(DMF)₄]·3DMF·CH₃OH (Ag₃₁S₂₀-DMF for short) (1) has been well-defined and characterized by FT-IR, PXRD, TGA, ¹H NMR and electronic absorption spectrum. Ag₃₁S₂₀-DMF contains a neutral [Ag₃₁S₃(S^tBu)₁₇(CF₃COO)₇(CO₃)_0.5(CF₃COOH)_0.5(DMF)₄] cluster, which is shaped in a turtle-like structure. MALDI-TOF MS analysis indicates that the [Ag₃₁S₃(S^tBu)₁₇(CF₃COO)₇(DMF)₄]⁺ cluster is chemically stable, and it can also associate with DMF and CH₃OH solvent molecules to be stable in solution at room temperature. Moreover, Ag₃₁S₂₀-DMF exhibits temperature-sensitive luminescence properties.