To meet the demands in portable electronic devices, electric vehicles and stationary energy storage, it is necessary to prepare advanced lithium ion batteries (LIBs) with high energy density and fast charge and discharge capabilities. Cathode materials, which account for 40%-50% of the cost of a whole battery, play a decisive role in cell voltage and capacity. Moreover, the performances of the cathodes are also balanced by many other aspects, including cycle life, rate capability, safety, costs, and environmental benignity. Unfortunately, none of the currently available cathode materials (e.g. LiFePO4, LiNi x Co y Mn1-x-y O2 layered oxides and Li-rich layered oxides) can get all the quests in a single cell. The electrochemical performances of a cathode are closely connected with its structural features, such as the porosities, morphologies and specifically exposed surfaces, which can be tuned by delicate designs. Here, we review our work on the rational design and delicate preparation of a series of cathode materials with controllable microstructures. We reveal the synergistic effects of both reaction and mass transfer on the formation of these meso-scale structures and the improved electrochemical performances of the cathode materials. The review will provide a scientific basis for the large-scale production of meso-scale structured cathode materials, and lay theoretical and experimental foundation for the application of cathode materials in next-generation LIBs.