To enhance the thermal properties of epoxy composites, expanded graphite (EG) was oxyfluorinated and embedded into epoxy resin as a reinforcement. The maximum thermal conductivity was obtained for epoxy composites with oxyfluorinated EG, representing a 62% increase compared to that of neat epoxy. Additionally, the glass transition temperature (Tg) and integral procedural decomposition temperature of epoxy composites with oxyfluorinated EG show the increase of 6% (4.4 °C) and 106% (264 °C), respectively, which indicated the improvement in thermal stability. These results can be attributed to the interfacial interaction between epoxy and oxyfluorinated EG, which formed strong interfacial interactions between the epoxy resin and EG due to the presence of oxygen- and fluorine-containing functional groups in oxyfluorinated EG.