To optimize the preparation process of graphene/cyanate ester (CE) composites and improve their toughness, p-phenylenediamine functionalized graphene oxide (GO-PPD) was prepared from graphene oxide (GO).GO/CE-epoxy and GO-PPD/CE-epoxy composites were prepared using CE and epoxy blends (mass ratio is 7:3) as matrix resin and GO, GO-PPD as addition filler.The chemical structure of GO and GO-PPD were characterized by FTIR and Raman spectroscopy.The solubility of GO and GO-PPD was also checked.GO-PPD can steadily dissolve in such solvents as alcohol with low boiling point and hypotoxicity.Compared with GO, GO-PPD greatly improves the preparation process of its composites.The property investigation shows that both of the introduction of GO and GO-PPD decrease the curing temperature, dramatically increase the mechanical and thermal properties, and increase the dielectric constant and the dielectric loss of the matrix resin obviously.However, the good hot-wet and corrosion resistance are maintained.The properties of graphene/CE-epoxy composites change with the surface chemical property of graphene.Compared with GO, GO-PPD more greatly contributes to the improvement of the mechanical and thermal properties of composites.