© 2020, The Author(s). Iron-based Prussian blue analogs are promising low-cost and easily prepared cathode materials for sodium-ion batteries. Their materials quality and electrochemical performance are heavily reliant on the precipitation process. Here we report a controllable precipitation method to synthesize high-performance Prussian blue for sodium-ion storage. Characterization of the nucleation and evolution processes of the highly crystalline Prussian blue microcubes reveals a rhombohedral structure that exhibits high initial Coulombic efficiency, excellent rate performance, and cycling properties. The phase transitions in the as-obtained material are investigated by synchrotron in situ powder X-ray diffraction, which shows highly reversible structural transformations between rhombohedral, cubic, and tetragonal structures upon sodium-ion (de)intercalations. Moreover, the Prussian blue material from a large-scale synthesis process shows stable cycling performance in a pouch full cell over 1000 times. We believe that this work could pave the way for the real application of Prussian blue materials in sodium-ion batteries.