Carbon-based anode materials hold a promising future for sodium-ion batteries (SIBs) due to their natural abundance and low cost of development. In spite of carbon's important role in the commercialization of lithium-ion batteries (LIBs), further exploration is necessary in order to find high-performance, high-rate carbon anode materials for SIBs. A honeycomb-like, nitrogen-rich (17.72 at%), hierarchically porous, and highly disordered carbonaceous material (N-HC) with an expanded interlayer distance (0.44 nm in average) is synthesized by spray drying and subsequent pyrolysis under flowing NH3. The hierarchically porous structure and rich nitrogen doping result in a large specific surface area (722 m2 g−1), more defects and active sites, and greater functional interface accessibility for the active porous carbonaceous material and electrolyte. When N-HC is used as the anode material for SIBs, the batteries display favorable discharge capacities (255.9 mA h g−1 in the 3000th cycle at 500 mA g−1) and good capacitive-energy-storage behavior (67% at a scan rate of 0.5 mV s−1) with excellent high-rate performance and ultra-stable cyclability over 10,000 cycles at 5000 mA g−1. Our results show that the combination of the hierarchically porous structure and nitrogen doping leads to improved energy storage by increasing the capacitive energy storage, which enhances the high-rate performance of N-HC. To further enhance the performance of the material, an electrical pretreatment is employed to increase the initial Coulombic efficiency of N-HC to 79.5%, a record high for an SIB cell. A full cell with an N-HC anode and a Na3V2(PO4)3/C cathode shows a high capacity with a favorable cyclability (238.7 mA h g−1 after 100 cycles at 100 mA g−1 and a capacity retention of 95.3% compared to the second cycle).