A detailed time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis of the lithium de-/ intercalation in thin films of the insertion cathode material lithium cobalt oxide is presented. The LiCoO2 (LCO) thin films are deposited by radio frequency magnetron sputtering at 600 degrees C, having a (003) preferred orientation after the deposition. The thin electrode films are cycled with liquid electrolyte against lithium metal, showing 80-86% extractable capacities. After disassembling the cells, the depth resolved elemental distribution in the LCO is investigated by ToF-SIMS and glow discharge optical emission spectroscopy. Both techniques show a stepwise lithium distribution in charged state, leading to a lithium depleted layer close to the surface. In combination with the electrochemical results, the qualitative comparison of the different lithium depth profiles yields a reversible lithium extraction in the depleted area below the stability limit for bulk materials of LCO. For bulk LCO, a phase change normally occurs when the lithium concentration in LixCoO(2) is lower than x = 0.5. As a possible cause for the inhibition of the phase change, the preferred orientation and thus pinning of the crystal structure of the film by the substrate is proposed. (C) 2016 Elsevier B.V. All rights reserved.