Practical Mg batteries still face significant challenges in their development, like the lack of simple compatible electrolytes, self-discharge, the rapid passivation of the Mg anode, and the slow conversion reaction pathway. Here, we propose a simple halogen-free electrolyte (HFE) based on magnesium nitrate (Mg(NO 3 ) 2 ), magnesium triflate Mg(CF 3 SO 3 ) 2 , and succinonitrile (SN) dissolved in acetonitrile (ACN)/tetraethylene glycol dimethyl ether (G4) cosolvents, with dimethyl sulfoxide as a functional additive. The addition of DMSO to the HFE changes the interfacial structure at the magnesium anode surface and facilitates the transport of magnesium ions. The as-prepared electrolyte shows high conductivity ( σ b = 4.48 × 10 −5 , 6.52 × 10 −5 and 9.41 × 10 −5 S cm −1 at 303, 323, and 343 K, respectively) and a high ionic transference number ( t mg +2 = 0.91/0.94 at room temperature/55 °C) for the matrix containing 0.75 ml of DMSO. Also, the cell with 0.75 ml of DMSO shows high oxidation stability, a very low overpotential, and steady Mg stripping/plating up to 100 h. Postmortem analysis of pristine Mg and Mg anodes extracted from disassembled Mg/HFE/Mg and Mg/HFE_0.75 ml DMSO/Mg cells after stripping/plating reveals the role of DMSO in improving Mg-ion passage through HFE by evolving the anode/electrolyte interface at the Mg surface. Further optimization of this electrolyte is expected to achieve excellent performance and good cycle stability when applied to the magnesium battery in future work. In this study, we design a functional halogen-free electrolyte by linking its active species with a high polarity dimethyl sulfoxide to reduce the solvation barrier of Mg 2+ .