Abstract [1, 4] Dithiino [2, 3-b]-1, 4-Dithiin (3) has been synthesised in high yield by a one- step procedure starting with sodium 1, 3-dithiole-2-thione-4, 5-dithiolate (2). The X-ray crystal structure shows non-planarity of the fused ring system as well as short intermolecular S ⃜S contacts.