Highly concentrated aqueous binary solutions of acetate salts are emerging as promising systems for advanced energy storage applications. Together with superior solubility of CH3COOK helpful in achieving water-in-salt electrolyte concentrations, the presence of CH3COOLi or CH3COONa permits intercalation of desired cations in electrode crystalline phases. Although these systems have captured profound scientific attention in recent years, a fundamental understanding of their physicochemical properties is still lacking. In this work, the thermal, rheological, transport, and electrochemical properties for a series of solutions comprising of 20 mol kg-1 of CH3COOK with different concentrations of CH3COONa are reported and discussed. The most concentrated solution, i.e., 20 mol kg-1 of CH3COOK with 7 mol kg-1 of CH3COONa came out to be the best in terms of a compromise between transport properties and electrochemical stability window. Such a solution has a conductivity of 21.2 mS cm-1 at 25°C and shows a stability window up to 3 V in “ideal” conditions, i.e., using small surface area and highly electrocatalytic electrode in a flooded cell. As a proof of concept of using this solution in sodium-ion batteries, carbon-coated LiTi2(PO4)3 (NASICON) demonstrated the ability to reversibly insert and de-insert Na+ ions at about -0.7 V vs. SHE with a first cycle anodic capacity of 85 mAh g-1, average charge efficiency of 96% at low current and a 90% capacity retention after 60 cycles. The very good kinetic properties of the interface are also demonstrated by the low value of activation energy for the charge transfer process (0.12 eV).