Au/Co multilayers were electrodeposited from a single bath based on acid citrate, cobalt sulphate and gold cyanide electrolyte. The Taguchi statistical method was used for experiment planning and optimisation. X-ray diffraction (XRD) investigations of the structure showed that the Au deposits exhibited a polycrystalline fcc <1 1 1> structure with an estimated grain size of similar to7 nm, while the Co deposits exhibited a nano-polycrystalline fcc structure with an estimated grain size ranging between 2 and 28 nm and a strong in-plane texture. The XRD investigation of the multilayer structure also indicated an interface roughness of about 1.5 nm between the Au and Co layers.