To improve the flame retardant performance of cellulose fibers, fluorine functional groups were introduced under various controlled fluorination conditions. The properties of the fluorinated cellulose fibers were analyzed by X-ray photoelectron spectroscopy and a thermogravimetric analysis. The fluorine functional group content in the fluorinated cellulose fibers increased with an increase in the fluorination temperature. However, the fluorination reaction increased the char yield and decreased the rate of degradation of the cellulose fibers by introducing donors, enabling the formation of a thick and compact char layer. Therefore, the flame retardant properties of cellulose fibers were improved following the fluorination treatment.