Severe plastic deformation (SPD) techniques are the best for producing of massive nanostructured materials. The methods of equal channel angular pressure (ECAP) and twist extrusion (TE) are realized by simple shear uniform deformation without change of cross-section sizes of sample. In the case of roll forming (RF) the shear strain is localized in the near-surface layer of metal. Intensity of shear strain in the near-surface layer depends on variation of parameters of deformation and conditions of friction in a contact. Steel 65G (0.65C, 0.3Si, 0.6Mn, 0.3Cr, and 0.3Ni) was deformed by roll forming. Transmission electron microscopy (TEM) of “cross-section” samples was used for studying of gradient structure of deformed material. TEM investigation shown that cell substructure in a near-surface layer have been formed. The depth of deformed layer is approximately 40 micrometers. Average cell size in cross-section direction is about 100 - 200 nm. Thin nanostructure layer with cell size about 20-30 nm was detected. In our opinion such substructure formed due to effect of “good” impurities.