The reaction of [NBuⁿ ₄][AuR₂](R = C₆F₅ or C₆F₃H₂-2,4,6) with Ag[ClO₄] leads to complexes [{AuAgR₂}_n], which react with neutral ligands to give complexes [{AuAgR₂L}_n](L = neutral O-, N-, S- or P-donor ligand, alkene, or alkyne). For R = C₆F₅ and L = diphenylacetylene, the product is [{AuAgR₂·0.5L}_n]; the 0.5L can be displaced by other ligands, such as acetone, arenes, or alkenes, to reform [{AuAgR₂L}_n]. An X-ray diffraction study of [{AuAgR₂L}_n](R = C₆F₅, L = tetrahydrothiophene) reveals (AuAg)₂ rings with Au–Ag 2.726 and 2.718 Å(the first reported Au–Ag bond lengths), linked by Au ⋯ Au short contacts (2.889 Å) to form infinite metal-atom chains. This complex crystallizes in space group Pccn, with a= 11.185(3), b= 22.475(6), c= 14.802(4)Å, Z= 8, R= 0.041 for 2 005 reflections. The complex [{AuAgR₂L}_n](R = C₆F₅, L = benzene) crystallizes in space group C2/c, with a= 24.231(5), b= 7.570(1), c= 22.613(5)Å, β= 117.49(2)°, Z= 8, and R= 0.035 for 3 008 reflections; it shows the same type of metal-atom chain (Au ⋯ Au 3.013; Au–Ag 2.702 and 2.792 Å). The benzene ring is co-ordinated by one edge to silver. In both structures the gold atoms lie on a crystallographic two-fold axis.