Plastic deformation of metallic materials up to large strains is, in many cases, characterised by the activation of different deformation modes and the formation of complicated, locally inhomogeneous substructures, which give rise to both significant lattice strains and rotations. A suitable tool for the investigation of the microstructures is a combination of diffraction techniques as, for instance, electron microscopy (TEM; EBSD) and X‐ray diffractometry. In order to demonstrate the potential of the diffraction analysis the following procedures are considered: Evaluation of radial and azimuthal broadening of X‐ray diffraction peaks, EBSD analysis of block structures, and TEM identification of disclination arrangements in compressed Fe–Si and Ni single crystals.