Low-cost graphite has emerged as the most promising anode material for potassium-ion batteries (PIBs). Constructing the inorganic-rich solid electrolyte interface (SEI) on the surface of graphite anode is crucial for achieving superior electrochemical performance of PIBs. However, the compositions of SEI formed by conventional strongly solvating electrolytes are mainly organic, leading to the SEI structure being thick and causing the co-intercalation behavior of ions with the solvent. Herein, a weakly solvating electrolyte is applied to weaken the cation-solvent interaction and alter the cation solvation sheath structures, conducing to the inorganic composition derived from anions also participating in the formation of SEI, together with forming a uniformly shaped SEI with superior mechanical properties, and thus improving the overall performance of PIBs. The electrolyte solvation structure rich in aggregated ion pairs (AGGs) (69%) enables remarkable potassium-ion intercalation behavior at the graphite anode (reversible capacity of 269 mAh g^-1) and highly stable plating/stripping of potassium metal anode (96.5%). As a practical device application, the assembled potassium-ion full-battery (PTCDA//Graphite) displays superior cycle stability. The optimizing strategy of cation solvation sheath structures offers a promising approach for developing high-performance electrolytes and beyond.