This paper presents the in situ mapping of temperature-dependent lithium-ion diffusion at the nanometer level in thin film Li1.2Co0.13Ni0.13Mn0.54O2 cathode using electrochemical strain microscopy. The thin-film Li1.2Co0.13Ni0.13Mn0.54O2 cathode exhibits higher lithium-ion diffusivities with increasing temperature, which explains the higher capacity observed in the lithium-ion batteries with a Li-rich cathode at elevated temperature. In addition, the activation energy for lithium-ion diffusion can be extracted in an Arrhenius-type plot at the level of grain structure with the assumption that the ionic movement is diffusion controlled. Compared with the grain interiors, the grain boundaries show relatively lower activation energy; hence, it is the preferred diffusion path for lithium ions. This study has bridged the gap between atomistic calculations and traditional macroscopic experiments, showing direct evidence as well as mechanisms for ionic diffusion for Li-rich cathode material.