The solvation of cations is one of the important factors that determine the properties of electrolytes. Rational solvation structures can effectively improve the performance of various electrochemical energy storage devices. Water-in-Salt (WIS) electrolytes with a wide electrochemically stable potential window (ESW) have been proposed to realize high cell potential aqueous electrochemical energy storage devices relying on the special solvation structures of cations. The ratio of H2O molecules participating in the primary solvation structure of a cation (a cation hydration ratio) is the key factor for the kinetics and thermodynamics of the WIS electrolytes under an electric field. Here, acetates with different cations were used to prepare WIS electrolytes. And, the effect of different cation hydration ratios on the properties of WIS electrolytes was investigated. Various WIS electrolytes exhibited different physicochemical properties, including the saturated concentration, conductivity, viscosity, pH values and ESW. The WIS electrolytes with a low cation hydration ratio (<100%, an NH4-based WIS electrolyte) or a high cation hydration ratio (>100%, a K-based WIS electrolyte and a Cs-based WIS electrolyte) exhibit more outstanding conductivity or a wide ESW, respectively. SCs constructed from active carbon (AC) and these WIS electrolytes exhibited distinctive electrochemical properties. A SC with an NH4-based WIS electrolyte was characterized by higher capacity and better rate capability. SCs with a K-based WIS electrolyte and a Cs-based WIS electrolyte were characterized by a wider operating cell potential, higher energy density and better ability to suppress self-discharge and gas production. These results show that a WIS electrolyte with a low cation hydration ratio or a high cation hydration ratio is suitable for the construction of power-type or energy-type aqueous SCs, respectively. This understanding provides the foundation for the development of novel WIS electrolytes for the application of SCs.