ABSTRACT Grain-boundary impurity diffusion of Au along the incoherent twin boundary in a diffusion-bonded Cu bicrystal has been studied by the serial sectioning technique. The measured penetration profiles had a rather atypical shape which we interpreted in terms of structural multiplicity of the grain-boundary structure. A method of processing such profiles has been suggested and the relative fraction of the grain-boundary structural modification exhibiting the lowest diffusion coefficient has been estimated as 60% . The difference between the energies of the two structural modifications has been estimated as being less than 17%, which is in good agreement with the results of computer simulations of the grain-boundary energy in Cu.