Inhomogeneous lithium (Li) deposition and unstable solid electrolyte interphase are the main causes of short cycle life and safety issues in Li metal batteries (LMBs). Developing a 3D structured matrix current collector and novel electrolyte are feasible strategies to tackle these issues. Ether-based electrolytes are widely used in LMBs. However, a fundamental understanding of Li-ion coordination and solvent remains incomplete. Here, lithiophilic Ag-Cu mesh is designed as the current collector to boost rapid Li-ion flux and Li metal nucleation. Meanwhile, dimethoxyethane (DME)/dioxolane (DOL) are used as complex solvents to enable lower interfacial resistance. The solvation structures at the interfaces of different collectors with different electrolytes are investigated. By applying in operando Raman spectroscopy, it is demonstrated that bis(trifluoromethylsulfonyl)imide TFSI