Reaction of N,N -ethylenebis(pyridin-2-thione) (EBPYT) with [Cu(MeCN) 4 ]PF 6 in acetonitrile/ethanol yields the complex {Cu 2 (EBPYT) 3 (PF 6 ) 2 } n which has been characterised by single crystal X-ray diffraction studies. The crystals are triclinic, space group P1, a = 7.552(2), b = 10.936(3), c = 15.039(4) , α = 110.93(2), β = 95.40(2), γ = 100.72(2)°, Z = 2. Each Cu(I) ion is tetrahedrally coordinated by four sulfur atoms, one from each of four different EBPYT ligands. Two of the sulfur atoms bridge pairs of copper atoms to form Cu 2 S 2 units. These are further linked by the EBPYT ligands to form novel chains of contiguous 18- and 36-membered rings.