We report the epitaxial growth of the LiNi1−y M y O2 films (M=Co, Co–Al) on heated nickel foil using pulsed laser deposition in oxygen environment from lithium-rich targets. The structure and morphology was characterized by X-ray diffractometry, electron scanning microscopy and Raman spectroscopy. Data reveal that the formation of oriented films is dependent on two important parameters: the substrate temperature and the gas pressure during ablation. The charge–discharge process conducted in Li-microcells demonstrates that effective high specific capacities can be obtained with films 1.35μm thick. Stable capacities of 83 and 92μAhcm−2 μm are available in the potential range 4.2–2.5V for LiNi0.8Co0.2O2 and LiNi0.8Co0.15Al0.05O2 films, respectively. The self-diffusion coefficient of Li ions determined from galvanostatic intermittent titration experiments is found to be 4×10−12 cm2 s−1.