A cathode based on micron-sized LiFePO4 (LFP) was used to highlight the possible improvements in the intrinsic limitations of poor electrical and ionic conductivity. So, these problems were overcomed to surface coating machanism that has provided a major breakthrough in high-performance electrodes of lithium-ion batteries (LIBs). This method with conductive materials at the level of single active particles has been used to challenge poor conductivity in electrodes. Nevertheless, the resulting decrease in the volumetric capacity and the complexity of the required manufacturing conditions are problematic for particle-scale coating techniques. Here, we report a facile alternative route to coating conformal thin-layer conducting poly(3,4-ethylenedioxythiophene) (PEDOT) through vapour reaction printing (VRP) on prepared LFP electrodes. The PEDOT coated LFP electrodes exhibited outstanding improvements in cycling stability and their rate capability compared with the uncoated pristine LFP electrode. These results were attributed to the conformal PEDOT layer, which offers improved conduction pathways and ion diffusion. Therefore, this new method of coating prepared LFP electrodes with a conductive conformal thin layer is providing for the design of electrodes for high-performance LIBs.