The preparation of copper(I) trifluoromethanethiolate, CF3SCu, in acetonitrile culminates in the crystallization of a discrete molecular aggregate complex containing ten copper thiolate units and eight molecules of acetonitrile with a central tritwistane core, as determined by single-crystal X-ray crystallography. Despite intensely active research in copper thiolate complexes due to the irrelevance to metalloproteins this appears to be the first structurally characterized neutral, solvated copper thiolate complex.