Abstract Aqueous lithium‐ion batteries are normally limited at low temperatures, because of the consequent low conductivity of electrolytes and the sluggish kinetics of electrode materials. Herein, a high‐performance ultra‐low temperature aqueous lithium ion‐bromine battery (ALBB) realized by a tailored functionalized electrolyte (TFE) consisting of lithium bromide and tetrapropylammonium bromide (TPABr) is reported, which can maintain liquid state with high conductivity (1.89 mS cm ‐1 ) at − 60 ° C. In addition, with the help of excellent bromine‐fixation of TPABr, the high reversible capacity can be provided by the fast redox reaction of Br 2 /Br ‐ couple in the cathode from room temperature (RT) to − 60 ° C. Moreover, 1,4,5,8‐naphthalenetetracarboxylic dianhydride‐derived polyimide anode can deliver excellent low‐temperature capacity retention as well as enhanced rate capability and reversibility at RT in TFE. As a result, the designed TFE can endow ALBB with high energy densities (98, 64, and 32 Wh kg dry ‐1 at RT, − 40, and − 60 ° C, respectively), outstanding power densities (24.6 and 1.2 kW kg dry ‐1 at RT and − 40 ° C, respectively), and superior capacity retentions (94% and 98% after running 1000 cycles at RT and − 40 ° C, respectively). This work demonstrates a novel strategy to widen the temperature range of aqueous batteries.