Controlling nanoscale structure and morphology of LiNi1/3Co1/3Mn1/3O2 (NCM) cathode material is essential to optimizing their electrochemical performance in rechargeable lithium batteries owing to their anisotropic Li ion transport behavior. Here we report novel nanoarchitectured NCM cathodes composed of self-assembled nanosheet structures synthesized via a facile hydrothermal method and a stepwise calcination process. The as-obtained NCM cathodes showed different surface architectures with various degrees of packing and tap densities, leading to very different Li ion transport kinetics and thus variable rate capability. This study shows a promising material model for detailed investigation of the fundamental relationship between the structures/morphologies of battery electrodes and their Li ion transport kinetics.