Analysis of the structural state of surface metal layers after their electrospark doping (ESD) and subsequent surface plastic deformation (SPD) has been performed. The structure levels and their scale ranging within 20–103 nm have been determined. Applying the methods of X-ray structure analysis and electron microscopy, it has been found that the linear defect density after ESD and after ESD SPD is practically identical; this allowed suggesting that the basis for the mechanism of plastic deformation of electrospark coatings is collective motion of dislocations, that is, rotational processes. Some ways of formation of stable and more homogeneous structures of electrospark coatings with required properties have been analyzed and proposed.