Nanostructured thin film electrodes have significant potential for enhancing the kinetics of lithium storage batteries and for providing optimal thickness for applications in lithium ion micro-batteries. In this research, LiNi0.8Co0.2O2 thin films are synthesized and deposited directly onto current collectors in a single step via a novel flame based method, namely reactive spray deposition technology (RSDT). The detailed surface morphology and size distribution of LiNi0.8Co0.2O2 particles are studied using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Electrochemical performance of the as-deposited LiNi0.8Co0.2O2 cathode is evaluated by galvanostatic charge-discharge measurement with a coin-type half-cell (CR2032). Data shows that the electrode delivers an initial discharge capacity of 50.84μAhcm−2 μm in the voltage window between 3.0 and 4.2V with a capacity retention rate of 83% after 50 cycles. The results are deemed promising as a pilot study and thus further optimization of processing conditions and electrode structures are worth pursuing.