The non-destructive structure characterisation of surface layers for various kinds of ball bearings can be a powerful method in surface characterization and in quality control. The ball bearings were made of 100Cr6 steel and they were superfinished and mechanically burnished. An application of classical X-ray diffraction sin2ψ method and classical Bragg-Brentano diffraction geometry in these kinds of surface examinations make some problems in term of X-ray real depth of penetration. An application of methods based on grazing angle X-ray diffraction geometry, made possible to get real value of residual macro-stresses, retained austenite and additionally could be suitable in estimation of their gradient-like distribution versus depth under surface. An application of this geometry to X-ray diffraction phase analysis enabled to get phase contents versus thickness under surface in non-destructive way as well. The results are not infected by gradient-like distribution. The X-ray quantitative phase analysis was used to establish volume fraction of transformed retained austenite. Theoretical calculation of residual macro-stresses due to volume fraction of transformed austenite in ball bearings and following measurements of residual stresses were curried out as well. The mechanical burnishing of ball bearings caused big compressive residual stresses about – 1000 MPa and phase transformation of austenite in thin surface layer. These factors can influence on properties of following exploitation and durability.