Aqueous sodium-ion batteries (AIBs) are promising candidates for large-scale energy storage due to their safe operational properties and low cost. However, AIBs have low specific energy (i.e., <80 Wh kg−1) and limited lifespans (e.g., hundreds of cycles). Mn-Fe Prussian blue analogues are considered ideal positive electrode materials for AIBs, but they show rapid capacity decay due to Jahn-Teller distortions. To circumvent these issues, here, we propose a cation-trapping method that involves the introduction of sodium ferrocyanide (Na4Fe(CN)6) as a supporting salt in a highly concentrated NaClO4-based aqueous electrolyte solution to fill the surface Mn vacancies formed in Fe-substituted Prussian blue Na1.58Fe0.07Mn0.97Fe(CN)6· 2.65H2O (NaFeMnF) positive electrode materials during cycling. When the engineered aqueous electrolyte solution and the NaFeMnF-based positive electrode are tested in combination with a 3, 4, 9, 10-perylenetetracarboxylic diimide-based negative electrode in a coin cell configuration, a specific energy of 94 Wh kg–1at 0.5 A g−1(specific energy based on the active material mass of both electrodes) and a specific discharge capacity retention of 73.4% after 15000 cycles at 2 A g−1are achieved.