AbstractHybridizing aqueous electrolytes with organic co‐solvents can effectively expand the voltage window of aqueous electrolytes while reducing salt usage, but most reported co‐solvents are usually flammable and toxic, hardly achieving compatibility between safety and electrochemical performance. Here, a new non‐flammable and non‐toxic low‐salt‐concentration (1.85 m) aqueous electrolyte is reported using the green co‐solvent isosorbide dimethyl ether (IDE). Owing to its unique 3D molecular structure, IDE can form a five‐membered ring structure by binding the Li ion. The steric hindrance effect from IDE weakens its solvation ability, generating anion‐participated solvation structures that produce a robust and uniform LiF‐rich solid electrolyte interphase layer while containing elastic IDE‐derived organics. Moreover, the multiple O atoms in IDE can effectively regulate the intermolecular hydrogen bonding networks, reducing H2O molecule activity and expanding the electrochemical window. Such unique solvation structures and optimized hydrogen bonding networks enabled by IDE effectively suppress electrode/electrolyte interfacial side reactions, achieving a 4.3 V voltage window. The as‐developed Li4Ti5O12(LTO)||LiMn2O4(LMO) full cell delivers outstanding cycling performance over 450 cycles at 2 C. The proposed green hybrid aqueous electrolyte provides a new pathway for developing high‐voltage aqueous lithium batteries.