Spontaneous reactions occurring at the surface of LiNi0.8Co0.2O2 and LiMn2O4-based electrodes during the storage in organic non-aqueous electrolytes have been investigated by diffuse reflectance FTIR technique. It is found that both materials spontaneously form different inorganic and organic compounds on their surface when in contact with electrolyte solutions. The nature of these self-acting reactions is moreover found to be similar to that of the processes occurring during electrochemical cycling of the electrodes. Reaction mechanisms and the final products depend on both electrode surface chemistry and the nature of electrolyte used. It appears that the spontaneous reactions are initiated by lithium deintercalation from the electrode active material. The influence of different factors, e.g. degree of lithiation of the active material, roughness of the electrode surface and temperature on the reaction rate is discussed.