The relationship between the graft yield and the effect of hexafluorobutyl methacrylate graft treatment on the structural changes of the silk fibers was studied on the basis of the results of scanning electron micrograph photographs (SEM), infrared spectroscopy (IR), Raman spectrum,wide-angle X-ray diffraction patterns (WAXD), nuclear magnetic resonance(NMR) and amion acid analysis. The results showed that the crystalline regions of grafted fibers were hardly affected and the fiber fission occurred on the cross sections of grafted fibers. The surface of fibers was covered with a high polymer film. The Raman spectrum showed there was little change in the conformation of grafted fibers which mainly remained β-sheet conformation. The IR of the grafted silk fibers showed new absorption of bands occurred which belonged to the stretching-vibrationabsorption-peak bands of VC=O and VC-F of aliphatic ester species. The CF3-,-CF2- and -CFH- structures of grafted silk macromdlecule were verified in the NMR spectrum.The amion acid analysis indicated fluoride monomers were inclined to graft with TYR,ARG and GLU of silk fibers.