Lithium bis(trifluoromethanesulphonyl)imide (LiTFSI) with outstanding electrochemical and thermal stability has promising applications in electrolytes for lithium batteries. However, a low concentration of the sulfonimide salt electrolyte can corrode a commonly used aluminum (Al) current collector, posing a perennial conundrum that hinders its wide application. In this work, we find that pure H2O as an additive in the 1 M LiTFSI electrolyte effectively protects the Al current collector from corrosion by TFSI−. The interface engineering by specific adsorption of H2O plays a pivotal role in regulating the structure of the electrical double layer on the Al foil surface, blocking the interaction of TFSI− with Al. Meanwhile, hydrogen bonds are verified between H2O and TFSI−, weakening the attack of TFSI− on the Al collector and improving the Li+ conductivity. The mechanism has been confirmed by theoretical calculations and a variety of characterizations. Benefiting from the addition of H2O, the lithium batteries exhibit excellent cycling performance at a high cut-off voltage of 4.4 V even at −20 °C and a 3 Ah pouch full cell shows long cycling performance. The results demonstrate the high compatibility of the H2O-added electrolyte with high voltage cathode, lithium metal and graphite anodes. This work introduces a strategy for the utilization of sulfonimide salt at high voltage and wide temperature even at a low concentration.