Multivalent (e.g., Mg²⁺, Ca²⁺ and Zn²⁺) metal cells using a nonaqeous electrolyte are potential candidates for post-lithium-ion batteries. However, the development of multivalent electrolytes is challenging due to its poor compatibility with both the metal anode and higher voltage cathode chemistries, leading to poor coulombic efficiency, formation of passivation layer on the metal anode, etc. Defining the connection between the electrochemical properties of a multivalent electrolyte system with its molecular scale structure is a crucial step for developing these new chemistries. Here we use X-ray absorption fine structure (XAFS) spectroscopy to determine the solvation structure of zinc-based electrolytes with varying solvent species and concentrations. To explore the role of ion-pairing, the results are compared to first principle simulations of the electrolyte and electrochemical data.