The basic principle of the X-ray diffraction analysis is based on the determination of components of residual stresses. They are determined on the basis of the change in the distance between atomic planes. The method is limited by a relatively small depth in which the X-ray beam penetrates into the analysed materials. For determination of residual stresses in the surface layer the X-ray diffraction and electrolytic polishing has to be combined. The article is deals with the determination of residual stress and real material structure of a laser-welded steel sample with an oxide surface layer. This surface layer is created during the rolling and it prevents the material from its corrosion. Before the X-ray diffraction analysis can be performed, this surface layer has to be removed. This surface layer cannot be removed with the help of electrolytic polishing and, therefore, it has to be removed mechanically. This mechanical procedure creates “technological” residual stress in the surface layer. This additional residual stress is removed by the electrolytic polishing in the depth between 20 and 80 μm. Finally, the real structure and residual stresses can be determined by using the X-ray diffraction techniques.