The past decades have witnessed the development of many technologies based on nanoionics, especially lithium-ion batteries (LIBs). Now there is an urgent need for developing LIBs with good high-rate capability and high power. LIBs with nanostructured electrodes show great potentials for achieving such goals. However, the nature of Li-ion transport behaviors within the nanostructured electrodes is not well clarified yet. Here, Li-ion transport behaviors in Li(x)CoO(2) nanograins are investigated by employing conductive atomic force microscopy (C-AFM) technique to study the local Li-ion diffusion induced conductance change behaviors with a spatial resolution of ~10 nm. It is found that grain boundary has a low Li-ion diffusion energy barrier and provides a fast Li-ion diffusion pathway, which is also confirmed by our first principles calculation. This information provides important guidelines for designing high performance LIBs from a point view of optimizing the electrode material microstructures and the development of nanoionics.