Iron fluorides based on conversion chemistry are developed as alternative cathode materials for Li-ion batteries due to their high capacity, also suffering from some drawbacks, such as poor electrical conductivity and structural instability. In order to improve the electrochemical performance of iron fluoride, in this work, we focus on the enhancement of the lithium extraction capability of FeF3 by introducing extra C@LiF additive. FeF3/C@LiF composites are fabricated by high energy ball milling. Due to the compact connection between LiF and conductive carbon in FeF3/C@LiF composites, LiF can not only act as high-active reactant for lithium extraction process, but also provide active sites for subsequent charge/discharge reaction. Electrochemical study results suggest that a suitable content of LiF enables FeF3/C@LiF composite to deliver a satisfactory electrochemical performance, which retain a capacity of 229mAhg−1 at a current rate of 40mAg−1 after 50cycles (10% higher than that of FeF3/C composite).