Surface nanocrystallization (SNC) is a novel method for improving materials properties. Nanostructured surface layers of about 20 μm thickness were produced in copper plate samples by means of surface mechanical attrition treatment (SMAT). The behaviors of the SMAT samples were investigated by using transmission electron microscopy (TEM), Vickers hardness testing and potentiodynamic anodic polarization tests. The experimental results showed that the longer the peening time was performed on the copper pate samples, the thicker the deformation layers formed. The microhardness results for the top surface layer of the copper plate sample are 1.723 GPa and 1.752 GPa for 45 and 60 min, respectively, which are about two times higher than that of the matrix. The primary passivate potential of nanocrystalline copper was more negative than that of coarse-grain copper.