This study reveals new surface chemistry in the dilute ether electrolyte -surface adsorbates matter to alter the solvent environment at a polarized cathode. This picture is qualitatively different from the high-/super-concentrated electrolytes, where their interfacial features inherit chemical signatures from bulk solution, namely, anions instead of solvent molecules dominated; while the interfacial chemistry of dilute electrolytes with additives in this study is primarily dominated by the oxidation of solvent molecules. Therefore, in the presence of additives, the purely anion-adsorption mechanism should start to become primary, highlighting the crucial role of anion-regulated interfacial feature rather than the nature of bulk solution on the solvent stability in the electrochemical device using dilute electrolytes.