A nanostructured surface layer with a gradient microstructure was produced on a Cu plate by means of the surface mechanical attrition treatment (SMAT). Diffusion of Ni in the nanostructured layer was investigated by the radiotracer technique at temperatures from 383 to 438 K. The measured diffusion profiles consist of two distinct sections with different slopes, the steep one corresponding to the top surface layer with the grain size of 10 to 25 nm and the shallow one corresponding to a subsurface layer with a grain size of 25 to 100 nm. The effective diffusivities derived from both sections are more than 2 orders of magnitudes higher than the grain boundary diffusivities in coarse-grained Cu. The significantly accelerated diffusion rates are expected to be associated with the “non-equilibrium” states of interfaces in the nanostructured surface layer induced by SMAT. The difference between the diffusivities in the top and sub- surface layer might result from the fact that most interfaces developed from twin boundaries in the former while produced by dislocation activities in the latter.