In this work, an ether‐based electrolyte is adopted instead of conventional ester‐based electrolyte for an Sb2O3‐based anode and its enhancement mechanism is unveiled for K‐ion storage. The anode is fabricated by anchoring Sb2O3 onto reduced graphene oxide (Sb2O3‐RGO) and it exhibits better electrochemical performance using an ether‐based electrolyte than that using a conventional ester‐based electrolyte. By optimizing the concentration of the electrolyte, the Sb2O3‐RGO composite delivers a reversible specific capacity of 309 mAh g−1 after 100 cycles at 100 mA g−1. A high specific capacity of 201 mAh g−1 still remains after 3300 cycles (111 days) at 500 mA g−1 with almost no decay, exhibiting a longer cycle life compared with other metallic oxides. In order to further reveal the intrinsic mechanism, the energy changes for K atom migrating from surface into the sublayer of Sb2O3 are explored by density functional theory calculations. According to the result, the battery using the ether‐based electrolyte exhibits a lower energy change and migration barrier than those using other electrolytes for K‐ion, which is helpful to improve the K‐ion storage performance. It is believed that the work can provide deep understanding and new insight to enhance electrochemical performance using ether‐based electrolytes for KIBs. By the optimization of solution and solute in electrolyte, Sb2O3‐RGO combined with a high‐concentration ether‐based electrolyte exhibits superior cycle life, stemming the suppression of by‐products in a battery. Furthermore, according to the density functional theory calculation, it is also found that the ether‐based electrolyte can accelerate the insertion of K‐ions, which is helpful to improve the K‐ion storage performance.