The incompatibility and immiscibility of natural rubber (NR)/fluoroelastomers (FKM) blends were improved by incorporation of a graft copolymer synthesized from the free radical graft copolymerization of 2,2,2-trifluoroethyl methacrylate (TFEM) onto NR initiated by benzoyl peroxide via a melt-mixing process. The grafting properties were investigated as functions of the initiator and monomer concentrations, reaction temperature and time. At the optimal conditions, the obtained graft NR (GNR) purified by Soxhlet extraction contained a maximum grafting efficiency of 1.34% with 49.1% monomer conversion. The structure of the purified GNR was analyzed using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and nuclear magnetic resonance spectroscopy (H-1 NMR and F-19 NMR). The gross GNR was then applied as the compatibilizer for NR/FKM vulcanizates (20/80 (w/w)) cured by peroxide vulcanization. The addition of GNR at 15 parts per hundred of rubber (phr) gave a vulcanizate with the highest tensile strength (9.93 MPa), some 5.31-fold higher than that of the incompatibilized one (1.87 MPa). This is likely to be due to the higher degree of homogeneity of the constituent phases in the GNR-compatibilized blends, as observed by scanning electron microscopy (SEM). The GNR-compatibilized NR/FKM vulcanizates were also resistant to gasohol E85 (85% (w/w) of ethanol). (C) 2013 Elsevier B.V. All rights reserved.