To fabricate reliable conducting matrix for highly insulated iron fluoride, we design a facile, green and low-cost solvothermal based synthesis method using graphene oxide powders and commercial FeF3·3H2O as precursors for the preparation of FeF3·0.33H2O/reduced graphene oxide (denoted as FeF3·0.33H2O/rGO) nanocomposite, as it is achieved by a combination of self-assembly, top-down phase transformation and solvothermal reduction processes. The 1D tunnel structure of FeF3·0.33H2O phase, nanoscale size and graphene conductive matrix together ensure ultrafast Li ion and electron transport. When applied as a cathode in lithium-ion batteries, the FeF3·0.33H2O/rGO electrode displays durable long-term cyclability (98% capacity retention over 100 cycles at 0.5C) and impressive rate capability (122 mAh g−1 at 10C), wherein surface-induced capacitive process plays an important role. Meanwhile, we also demonstrate the successful preparation of FeF2/reduced graphene oxide (denoted as FeF2/rGO) nanocomposite through adaption of reaction temperature, which has been seldom synthesized and here also exhibits high electroactivity.