Energy-filtering transmission electron microscopy (EFTEM) analysis coupled with the technique of samples preparation, focused ion beam, was used to study physical, chemical, and mechanical properties of diamond-like carbon coatings (DLCs). Two different coatings (ta-C and a-C:H) were investigated, presenting different tribological behaviors in a boundary lubrication regime with glycerol. Electron energy loss spectroscopy appears to be a very powerful technique to characterize such DLC coatings. Special attention was paid to the maximum energy of the plasmon peak, which was used to evaluate some physical and mechanical properties of DLC coatings (density, s p3 s p2 ratio, hardness). For ta-C superlubric coating, EFTEM results show a rearrangement of the DLC bulk structure under the friction process. Typically, the transformation of s p3 carbon into s p2 carbon was clearly observed and permits a self-adaptation of the coating, allowing it to support shearing without any delamination in spite of important compressive residual stresses in the coating. Moreover, the formation of graphitic carbon is evidenced at the top surface. This graphitic layer certainly helps the lubrication by glycerol in forming OH termination.