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The matrix of poly(fluorinated ethylene‐propylene) (FEP) was modified with graphene (GE) as filler, and then the composite fibers were prepared by melt spinning method with a twin‐screw extruder. The effects of both the draw ratio and GE content on the structures and properties of FEP/GE composite fibers were investigated. The results showed that the addition of nanoparticles reduced the crystallization of molecular chains and the orientation of crystalline units in the fibers, while the drafting and heat setting process could effectively improve the crystallinity and orientation of composite fibers. Moreover, the addition of GE improved the mechanical properties of the composite fibers and had no effect on the chemical resistance of the composite fibers. A significant enhancement of mechanical properties of the composite fibers was obtained at low GE content, that, a 35.5% improvement of tensile strength and a 19.5% increase of Young's modulus were achieved at a GE content of only 0.3 wt%. Compared with pure FEP fibers, the oil affinity of composite fibers was also significantly improved. The prepared FEP/GE composite fibers that showed excellent chemical resistance have potential application in oil‐water separation, especially in high temperature resistant fibrous materials. [ABSTRACT FROM AUTHOR]