We report the synthesis, optical spectrum, and crystal and electronic structures of a new organic-inorganic hybrid compound, [(p-NH3C6H4)(2)CH2](4) [(AuI2)(AuI4)(I-2)(2)(I-5)(2)Cl-4], with unique mixed-valent gold(I/III) chains. The chains feature face-shared octahedral [(AuAuI6)-Au-I-I-III](2-) units and are embedded within polyiodide layers. The new mixed-valent gold iodide crystallizes in the orthorhombic space group Pnnm, with a = 27.0703(2), b = 8.9363(5), c = 18.4280(1) Angstrom, Z = 2, and exhibits an optical band gap of 0.53 eV.