High-capacity cathode materials of metal fluorides generally undergo low conductivities and sluggish kinetics derived from a multielectron-transfer conversion reaction mechanism, which severely hinder the cycling stability and rate performance towards their commercialization. Herein, a flexible free-standing FeF₃/chitosan pyrolytic carbon/reduced graphene oxide (FeF₃/C/RGO) film as an additive-free cathode was designed and prepared by a facile hydrothermal strategy followed by sequential freeze-drying, thermal reduction and fluorination post-treatments. The ultrafine FeF₃ nanoparticles (NPs, ~30 nm) are confined within highly ordered RGO film, effectively reducing the Li⁺ diffusion pathway while the RGO sheets act as a matrix to restrict the complicated interlamination reaction (Fe³⁺⇄Fe²⁺⇄Fe) between adjacent interlayers with the spacing of ~30 nm. Benefiting from the free-standing structure, the FeF₃/C/RGO film can achieve an admirable capacity up to 220 mAh g^–1 over 200 cycles at 100 mA g^–1, showing great potential for wearable and flexible electronic devices.