To achieve this goal, we develop a strategy based on anion adsorption to alter the ether solvent environment within the electrical double layer (EDL) at the cathode. This strategy enables the enhancement of oxidation stability in 1 M imide salt-based 1,2-dimethoxyethane (DME) electrolytes up to 4.3 V, only by adding a small amount of nitrate. The LMBs coupled with high-voltage LiCoO2 and NMC532 cathodes in these dilute ether electrolytes exhibit superior cycling stability. Although many promising properties of nitrate for Li metal anodes have been reported, very limited progress has been made on nitrate interfacial behavior near the cathode surface. Here, experimental measurements and molecular simulations were combined to elucidate that by regulating the interfacial structure at the cathode, added NO3 -could suppress the ether oxidative decomposition, although the additive has little influence on the bulk electrolyte. As a proof of concept, beyond NO3 -, we experimentally demonstrated that a series of anions, including ClO4 -, ClO3 -, H2PO4 -and HPO4 2-, have similar effects on improving the oxidation stability of ethers. This electrolyte design concept would provide insights into the high-voltage application of low concentration electrolytes in LMBs.