The drawbacks of temperature sensitivity, high voltage intolerance, and flammability of lithium batteries are gradually brought to light in conventional carbonate electrolytes. To solve these problems, a localized high concentration electrolyte (LHCE) employing highly fluorinated ethyl trifluoroacetate (TFAE) and 2,2,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy) propane (TFEP) is designed. When applied in high-energy lithium batteries, the discharge specific capacity of Li||NMC811 battery can maintain 143.6 mAh/g after 500 cycles at 4.6 V and 1C, and the capacity retention of Li||LNMO battery retains as high as 89.99 % after 500 cycles at 5 V. In addition, this LHCE also possesses the ability to operate the battery under challenging conditions including low temperature, fast charge, safety risks, etc. The LHCE based on TFAE and TFEP has unique solvated structures to generate a moderate LiF-rich interfacial layer, ensuring the fast Li+ migration. This work will provide strong guidance for future electrolyte industrial design of high-energy lithium battery.