The liquid lithium/(LiCl-KCl eutectic melt) interface was studied using electroanalytical techniques (chronopotentiometry, cyclic voltammetry and electrochemical impedance spectroscopy). The formation of a Li2Cl layer has been shown and the role of residual oxide ions has been investigated. Results allow us to clarify the mechanism that leads to the formation of a Li2Cl layer at the interface as well as its evolution with time.