Sodium-ion batteries (SIB) require high-power, long-lasting cathode materials for optimal performance. Cathodes consisting of layered sodium transition metal oxides are typically used. In article number 1400458, Christopher S. Johnson and co-workers demonstrate that the electrochemical properties largely depend on their layer-stacking structures. Novel composite layered oxide materials that feature layers that are intergrown and have orientation relationship are synthesized. The various stacking sequences work in tandem to synergistically improve the cathode performance in SIBs.