Considering that the electrolyte reactivity originates from the solvent contacting the cathode, a thorough understanding of the aggregation state of different solvent molecules or ions at the electrified interface becomes very crucial. MD simulations with the implementation of the constant potential method for asymmetric electrode systems with Li metal anode and LiCoO2 cathode, depicted in Figure , were adopted to dissect the EDL structure of pristine and NO3 --containing 1 M LiTFSI in DME at the cathode. For the pristine ether electrolyte, under the positive polarization, a distinct layer of DME molecules within ~0.5 nm could contact the cathode (Figure ), with the vector between two O atoms of a DME molecule mainly parallel to the cathode surface (Figure ); while with adding a small amount of NO3 -, the DME at the cathode is found to be drastically reduced, as illustrated in Figure . Meanwhile, a large accumulation of NO3 -anions can be found at the cathode surface, driven by the positive polarization (Figure ); interestingly, the number ratio of interfacial NO3 -to TFSI -is 0.83 (from the integration of number density in Figure ), which is far above the ratio in the bulk region (0.2), this remarkable increase of NO3 -anions at interface implies the preferential absorption of NO3 -for LiCoO2. More importantly, this finding indicates that the interfacial features of NO3 --containing ether electrolyte does not inherit chemical signatures from bulk solution, which is qualitatively different from the high-/super-concentrated electrolytes . This preferential absorption of NO3 -can be explained by the lower free energy of interfacial NO3 -than TFSI -(Figure ), which may result from the geometric shape/size of anions and delocalized intrinsic charge of the cathode (Figures and). However, the Li + ion peak becomes unexpectedly higher, which could be understood by the attraction from accumulated NO3 -anions and their strongest interaction with Li + (Figure ). At higher electrode polarization (2.0 V), a similar response is detected for the presence of anions, cations, and DME molecules (Figure ).