The interfacial instabilities, including side reactions due to electrolyte decompositions and Cobalt (Co) dissolutions, are the main detrimental processes at LiCoO2 cathode when a high-voltage window (>4.2 V) is applied. Nevertheless, cycling the cathode with a voltage above 4.2 V would deliver an increased gravimetric capacity, which is desired for high power battery operation. To address these drawbacks, we demonstrate a synergistic approach by manufacturing the three-dimensional high-temperature LiCoO2 electrodes (3D HT-LCO) using laser-microstructuring, laser-annealing and subsequent coating with polymerized C60 thin films (C60@3D HT-LCO) by plasma-assisted thermal evaporation. The C60@3D HT-LCO cathode delivers higher initial discharge capacity compared to its theoretical value, i.e. 175 mA h g−1 at 0.1 C with cut-off voltage of 3.0–4.5 V. This cathode combines the advantages of the 3D electrode architecture and an advanced C60 coating/passivation concept leading to an improved electrochemical performance, due to an increased active surface area, a decreased charge transfer resistance, a prevented Co dissolution into the electrolyte and a suppressed side reaction and electrolyte decomposition. This work provides a novel solution for other cathode materials having similar concerns in high potential regimes for application in lithium-ion microbatteries.