Lithium-ion batteries (LIBs) have been extensively investigated due to the ever-increasing demand for new electrode materials for electric vehicles (EVs) and clean energy storage. A wide variety of nano/microstructured LIBs electrode materials are hitherto created via self-assembly, ranging from 0D nanospheres; 1D nanorods, nanowires, or nanobelts; and 2D nanofilms to 3D nanorod array films. Nanoparticles can be utilized to build up integrated architectures. Understanding of nanoparticles’ self-assembly may provide information about their organization into large aggregates through low-cost, high-efficiency, and large-scale synthesis. Here, the focus is on the recent advances in preparing hierarchically nano/microstructured electrode materials via self-assembly. The hierarchical electrode materials are assembled from single component, binary to multicomponent building blocks via different driving forces including diverse chemical bonds and non-covalent interactions. It is expected that nanoparticle engineering by high-efficient self-assembly process will impact the development of high-performance electrode materials and high-performance LIBs or other rechargeable batteries.