Copper(I) iodide on recrystallization from neat pyridine yields a 1 : 2 adduct; it is established by single-crystal X-ray diffraction methods at 295 K that this is a ��'-diiodobridged dimer, with four- coordinate copper(I), [(py)2CuI2Cu(py)2]. Crystals are orthorhombic, C2221, a 14.578(4), b 10.448(3), c 31.559(7) �, Z = 8 dimers. Cu. . .Cu is 2.699(5) �.