Cathode wear in aluminum electrolysis cells is an undesired phenomenon which decreases potlife. Although it has been the subject of many studies, it is not yet satisfactorily understood. Furthermore, one major factor of this wear is the formation and dissolution of aluminum carbide, for which the mechanisms also still remain to be thoroughly explained. In view of this, laboratory scale electrolysis experiments were performed under different operating conditions, namely the duration and the presence or absence of an aluminum metallic layer on the cathode surface. The aluminum carbide formation was then studied using tomography, optical microscopy, Scanning Electron Microscopy- Energy Dispersive Spectroscopy (SEM-EDS) and X-ray Photoelectron Spectroscopy (XPS). In particular, the XPS analysis permits further investigation of the chemical species present in bath-penetrated veins of the carbon cathode.