Popularly-used fluorination can effectively weaken Li+-solvent interaction to facilitate the desolvation process at low temperature; however, high fluorination degree sacrifices salt dissociation and ionic conductivity. Herein, functional fluorinations are well tuned with different amounts of F atoms to balance Li+-solvent binding energy and ion movement, which reveals the fluorination effect on the solvation behavior and low-temperature performance. Noteworthily, the moderately-fluorinated ethyl difluoroacetate (EDFA) successfully favors a lower binding energy than less-fluorinated ethyl fluoroacetateand superior salt dissociation more than highly-fluorinated ethyl trifluoroacetate, realizing the trade-off between weak affinity and sufficient ionic conductivity. The well-formulated EDFA-based electrolyte exhibits a unique solvation sheath and generates inorganic-rich solid electrolyte interphase with low resistance for smooth Li+ diffusion, which enables graphite anodes with excellent fast-charging capability (196 mAh g−1 at 6 C) and impressive low-temperature performance with a reversible capacity of 279 mAh g−1 under −40 °C. Subsequently, the wide electrochemical potential window of EDFA-based electrolyte endows the 1.2 Ah LiNi0.8Co0.1Mn0.1O2 (NCM811)||graphite pouch cells with a high reversible capacity retention of 58.3% at −30 °C and discharge capacity of 790 mAh at −40 °C. Such solvent molecules with a moderately-fluorinated strategy promise advanced electrolyte design for lithium-ion batteries operating under harsh conditions.