This study shows the experimental data obtained by Raman spectroscopy to evaluate the structural changes of vegetable lubricants modified with montmorillonite after tribological tests. The analysis of the friction factor and limiting load of wear in the test for the examined grease compound shows a substantial effect on this parameter for grease. A change in the evaluated tribo-parameter results in a modification of the structure of the tested lubricant and changes in the protection efficiency of the tribological system. The amount of thickener, oil base and additive in the grease structure has an influence on the value of anti-wear properties, as shown by the data obtained in the tribological test described in this paper. The Raman spectroscopy tests showed that, in the tribological processes, some of the ingredients undergo an oxidative reaction, which leads to the formation of oxygenated organic substances that form an organic layer on the metal surface and counteract the wear of the lubricated contact surfaces. Other compounds come into close contact with the tribological layer, which increases its ability to resist wear and shear. The efficiency of the used additive is based on the formation (during friction) of a low-shear and high-plastic-strength thin film which is chemically highly bonded to the material and has a high level of durability against wear processes. As a consequence of the thermal decomposition of the additive, chemical interactions occur among the ingredients of the material of the substrate and the lubricants.