As a promising energy storage system, sodium-ion batteries face challenges related to the stability and high-rate capability of their electrode materials, especially carbon, which is the most studied anode. Previous studies have demonstrated that three-dimensional architectures composed of porous carbon materials with high electrical conductivity have the potential to enhance the storage performance of sodium-ion batteries. Here, high-level N/O heteroatoms-doped carbonaceous flowers with hierarchical pore architecture are synthesized through the direct pyrolysis of homemade bipyridine-coordinated polymers. The carbonaceous flowers could provide effective transport pathways for electrons/ions, thus allowing for extraordinary storage properties in sodium-ion batteries. As a consequence, sodium-ion battery anodes made of carbonaceous flowers exhibit outstanding electrochemical features, such as high reversible capacity (329 mAh g−1at 30 mA g−1), superior rate capability (94 mAh g−1at 5000 mA g−1), and ultralong cycle lifetimes (capacity retention rate of 89.4% after 1300 cycles at 200 mA g−1). To better investigate the sodium insertion/extraction-related electrochemical processes, the cycled anodes are experimentally analyzed with scanning electron microscopy and transmission electron microscopy. The feasibility of the carbonaceous flowers as anode materials was further investigated using a commercial Na3V2(PO4)3cathode for sodium-ion full batteries. All these findings indicate that carbonaceous flowers may possess great potential as advanced materials for next-generation energy storage applications.