Creating new nanostructured materials inspired by biomaterials is one of the most fascinating topics owing to their fantastic properties. Herein, we synthesize a new hollow aurilave-like carbon using the natural spores of Lycoperdon Boavista (SLBs) as hard-template, where the heteroatom of nitrogen and oxygen can be in-situ doped simultaneously. The hollow N/O-co-doped carbon (HNOC) has a high specific surface area and is rich in defects, enabling high performances in sodium-ion batteries (SIBs) and supercapacitors (SCs). A high sodium storage capacity of 246 and 107 mAh g−1 with superior stability over 1000 cycles can be achieved at the rates of 0.1 and 2 A g−1, respectively. Besides, the high rate capacity of 260 F g−1 at 5 A g−1 and extraordinary cycling stability over 10,000 cycles are also demonstrated in SCs. The great features of HNOC are further studied versus Na3V2(PO4)3 cathode in a sodium ion full battery, where the excellent stability and span life are both confirmed. We hope this newly-designed carbon material could complement the structure-related properties in electrochemistry, and also the presented synthetic strategy can be widely extended for designing more functional materials with greater capabilities.