A 3D hierarchical meso- and macroporous Na3V2(PO4)3-based hybrid cathode with connected Na ion/electron pathways is developed for ultra-fast charge and discharge sodium-ion batteries. It delivers an excellent rate capability (e.g., 86 mA h g(-1) at 100 C) and outstanding cycling stability (e.g., 64% retention after 10,000 cycles at 100 C), indicating its superiority in practical applications.