Homogeneous LiF/Fe/Graphene nanocomposites as cathode material for lithium ion batteries have been synthesized for the first time by a facile two-step strategy, which not only avoids the use of highly corrosive reagents and expensive precursors but also fully takes advantage of the excellent electronic conductivity of graphene. The capacity remains higher than 150 mAh g-1 after 180 cylces, indicating high reversible capacity and stable cyclability. The ex-situ XRD and HRTEM investigations on the cycled LiF/Fe/G nanocomposites conform the formation of FeFx and the coexistence of LiF and FeFx at the charged state. Therefore, the heterostructure nanocomposites of LiF/Fe/Graphene with nano-LiF and ultrafine Fe homogeneously anchored on graphene sheets could open up a novel avenue for the application of iron fluorides as high performance cathode materials for lithium ion batteries.