In nonaqueous Mg batteries, inactive adsorbed species and the passivation layer formed from the reactive Mg with impurities in the electrolyte seriously affect the Mg metal/electrolyte interface. These adlayers can impede the passage of Mg$^{2+}$ ions, leading to a high Mg plating/stripping overpotential. Herein, we report the properties of a new additive, bismuth triflate (Bi(OTf)$_{3}$), for synthesizing a chlorine-free Mg electrolyte to enhance Mg plating/stripping from initial cycles. The beneficial effect of Bi(OTf)$_{3}$ can be ascribed to Bi/Mg$_{3}$Bi$_{2}$ formed in situ on the Mg metal surface, which increases the charge transfer during the on–off transition by reducing the adsorption of inactive species on the Mg surface and enhancing the resistance of the reactive surface to passivation. This simple method provides a new avenue to improve the compatibility between the Cl-free Mg electrolyte and the Mg metal anode.