A theoretical model is suggested which describes the transformations of grainboundary dislocation walls and their influence on diffusion processes in nanocrystalline materials fabricated under highly non-equilibrium conditions. It is shown that the decay of boundary dislocation walls of finite extent, occurring via the climb of boundary dislocations and the corresponding emission of vacancies, is capable of highly enhancing the grain-boundary diffusion in nanocrystalline materials. The enhanced diffusion, in turn, strongly affects the deformation behaviour of nanocrystalline materials. In the case of nanocrystalline films deposited on to substrates, the effects of misfit stresses on the transformations of boundary dislocation walls and the diffusion are analysed. It is demonstrated that the mean diffusion coefficient in a nanocrystalline film may increase by approximately several orders of magnitude owing to misfit stresses. } 1. Introduction In recent years, nanocrystalline materials have attracted tremendous attention motivated by their wide applications in advanced technologies (for example Chow et al. (2000), Gleiter (2000) and Roco et al. (2000)). Of special interest, from both fundamental and applied viewpoints, are the specific peculiarities of diffusion in nanocrystalline materials which crucially affect their outstanding mechanical and sensing characteristics. Following Horvath et al. (1987), Gleiter (1989, 2000, Schaefer et al. (1995) and Kolobov et al. (1999Kolobov et al. ( , 2000, nanocrystalline materials exhibit anomalously enhanced diffusion properties. For instance, the boundary diffusion coefficients in bulk nanocrystalline materials fabricated by high-pressure compaction and severe plastic deformation methods are several orders of magnitude larger than those in conventional polycrystalline materials with the same chemical composition (Horvath et al.