Pore-structure design with increased ion-diffusion ability is usually regarded as an effective strategy to improve K-storage performance in hard carbon (HC). However, the relationship between porous structure and K + migration behavior remains unclear and requires further exploration. Herein, a series of chemically activated hard carbon spheres (denoted as AHCSs) with controllable micro/mesopores structure are successfully synthesized to explore intercorrelation between micro/mesopores and K migration behavior. The experimental results indicate AHCSs have two different K + storage ways, that is, adsorption behavior at high potential region and intercalation process at low potential region. These behaviors are closely related to the pores structure evolution: the micropores afford extra active sites for efficient K-ions adsorption, and therefore positive correlation between micropores and adsorption-contributed capacity is confirmed; the mesopores permit more K-ions intercalation/deintercalation by offering adequate pathways, and as a result positive correlations between mesopores and intercalation-contributed capacity as well as initial Coulombic efficiency are revealed. All these together contribute to achieving excellent reversible capacity, and exceptional rate capability with an ultra-long cycle lifespan in PIBs, and simultaneously exhibit a high energy density as well as considerable cycling stability for potassium-ion full cells. These results promote a fundamental understanding of K + migration behaviors in hard carbon.