A new copper(I)–thiolate (Cu–S) cluster with a CsCl unit (1, [Cu₁₂(μ₄-SCH₃)₆(NH₃)₁₂][Cu₁₂(μ₄-SCH₃)₆Cl₁₂]) exhibited interesting mechanochromic and thermochromic luminescence properties. Additionally, heteroatom-rich 1 could also be used as an electrocatalyst for the oxygen evolution reaction in alkaline media. The supersalt-type Cu–S cluster for the first time realized mechano/thermochromic and electrocatalytic applications.