Layered LiNi1/3Co1/3Mn1/3O2 thin film electrodes are successfully prepared by pulsed laser deposition technique and post-annealed. The microstructure of the thin films is characterized by X-ray diffraction, field emission scanning electron microscopy, X-ray photoelectron spectroscopy and transmission electron microscopy. The electrochemical performance of the thin film electrodes is evaluated by cyclic voltammetry and galvanostatic charge–discharge measurements. The kinetics of Li diffusion in the thin film electrodes are investigated by galvanostatic intermittent titration technique. The annealed thin films exhibit a partially amorphous structure. The electrochemical performance of LiNi1/3Co1/3Mn1/3O2 thin film electrodes depends on the annealing temperature, composition and thickness. The thin film electrodes deposited for 30 min with the annealing temperature of 450 °C deliver the best electrochemical performance, including high capacities, good cycle performance and rate capability. The initial discharge capacity of the thin film electrodes is 177 mAh g−1 measured at a rate of 0.1C in the voltage range of 2.8–4.5 V. The capacity retention ratio is 92% after 25 cycles at 0.5C rate. The chemical diffusion coefficients of lithium ion in the thin film electrodes are in the range of 10−9–10−10 cm2 s−1.