In modern society, advanced technology has facilitated the emergence of multifunctional appliances, particularly, portable electronic devices, which have been growing rapidly. Therefore, flexible thermally conductive materials with the combination of properties like outstanding thermal conductivity, excellent electrical insulation, mechanical flexibility, and strong flame retardancy, which could be used to efficiently dissipate heat generated from electronic components, are the demand of the day. In this study, graphite fluoride, a derivative of graphene, was exfoliated into graphene fluoride sheets (GFS) via the ball-milling process. Then, a suspension of graphene oxide (GO) and GFSs was vacuum-filtrated to obtain a mixed mass, and subsequently, the mixed mass was subjected to reduction under the action hydrogen iodide at low temperature to transform the GO to reduced graphene oxide (rGO). Finally, a highly flexible and thermally conductive 30-μm thick GFS@rGO hybrid film was prepared, which showed an exceptional in-plane thermal conductivity (212 W·m·K) and an excellent electrical insulating property (a volume resistivity of 1.1 × 10 Ω·cm). The extraordinary in-plane thermal conductivity of the GFS@rGO hybrid films was attributed to the high intrinsic thermal conductivity of the filler components and the highly ordered filler alignment. Additionally, the GFS@rGO films showed a tolerance to bending cycles and high-temperature flame. The tensile strength and Young's modulus of the GFS@rGO films increased with increasing the rGO content and reached a tensile strength of 69.3 MPa and a Young's modulus of 10.2 GPa at 20 wt % rGO. An experiment of exposing the films to high-temperature flame demonstrated that the GFS@rGO films could efficiently prevent fire spreading. The microcombustion calorimetry results indicated that the GFS@rGO had significantly lower heat release rate (HRR) compared to the GO film. The peak HRR of GFS@rGO10 was only 21 W·g at 323 °C, while that of GO was 198 W·g at 159 °C.