Defects engineering is an attractive strategy to improve the potassium storage performance of carbon anodes. The current studies mainly focus on the introduction of external defects via heteroatom doping, however, the exploration on the effect of intrinsic defects caused by the loss of atoms or distortion in the crystal lattice on potassium storage is still lacking to date. Hence, a series of carbon materials with different intrinsic defect levels are developed via a soft-template assisted method. It is found that intrinsic defects content in carbon is synergistically determined by the application of template and pyrolysis temperature, and a higher defects content is more likely to expose enormous edge active sites. This greatly promotes K-adsorption storage during surface-induced capacitive process, and therefore a strong positive correlation between capacity/capacity retention and intrinsic defects content is confirmed. As a result, the electrode with maximum defects content realizes a good capacity and a rate capability with long cycle lifespan (225.9 mAh g −1 at 2 A g −1 over 2000 cycles). This study offers an insight into the role of intrinsic defects of carbon materials in potassium storage performance.

Multipores engineering composed of micro/mesopores is an effective strategy to improve potassium storage performance via providing enormous adsorption sites and shortened ions diffusion distance. However, a detailed exploration of the role played by macropores in potassium storage is still lacking and has been barely reported until now. Herein, a superstructure carbon hexahedron (DGN‐900) is synthesized using poly tannic acid (PTA) as precursor. Due to the spatially confined two‐step local contraction of PTA along different directions and dimensions during pyrolysis, defective nanosheets with macropores are formed, while realizing a balance between defects content and graphitization degree by regulating temperature. The presence of macropores is conducive to accelerating electrolyte ions rapid infiltration within electrode, and its pore volume can accommodate electrode structure fluctuation upon cycling, while the most suitable ratio of defects to graphitic provides rich ions adsorption sites and sufficient electrons transfer channels, simultaneously. These advantages enable a prominent electrochemical performance in DGN‐900 electrode, including high rate (202.9 mAh g −1 at 2 A g −1 ) and long cycling stability over 2000 cycles. This unique fabrication strategy, that is, defects engineering coupled with macropores structure, makes fast and durable potassium storage possible.