The Copper(Ⅰ) supramolecular complexes of 4,5-bis(methylthio)-1,3-dithiole-2-thione (C5H6S5), [Cu(C5H6S5)(SCN)]∞ 1 and [Cu(C5H6S5)I]∞ 2, have been prepared and characterized. X-ray structure analysis for complex 1 reveals that the infinite chain structure with polymeric stairs of different lengths is formed through the coordination mode (μ3) of the thiocyanate bridges. The shorter interchain S...S contacts give rise to a three-dimensional network structure. CCDC: 215668. The Copper (Ⅰ) supramolecular complexes of 4,5-bis (methylthio) -1,3-dithiole-2-thione (C5H6S5), [Cu (C5H6S5) (SCN)] ∞ 1 and [Cu (C5H6S5) I] ∞ 2, have been prepared and characterized. X-ray structure analysis for complex 1 reveals that the infinite chain structure with the polymeric stairs of different lengths is formed through the coordination mode (μ3) of the thiocyanate bridges. The shorter interchain S ... S contacts give rise to a three-dimensional network structure. CCDC: 215668.