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 °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 LixCoO2 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.