Spontaneous reactions occurring at the surface of LiNi y Co(1−y)O2-based electrodes during contact with non-aqueous organic electrolytes have been investigated by FTIR and Raman spectroscopy. It is found that several types of compounds and/or functional groups are formed on the electrode surface and that these compounds appear to be dependent on the type of electrolyte used. Thus, for a LiClO4-propylene carbonate (PC) electrolyte, the main reaction is formation of Li-carbonate, whereas in the case of LiPF6-ethylene carbonate/dimethyl carbonate (EC/DMC) electrolyte formation of P-, O- and F-containing compounds dominate. Spectroscopic data also show a variation of the LiNi(1−y)Co y O2 crystalline structure during storage in an electrolyte which probably is due to a spontaneous deintercalation of the Li ions. An analysis of the newly formed species is presented and possible reaction mechanisms are discussed.