Graphene oxide (GO) was made by a modified Hummers method. Graphene oxide modified phenolic resin nanocomposites (GO/PF) were prepared by Steglich esterification, catalyzed by dicyclohexyl carbodiimide and 4-dimethylaminopyridine. The composites were characterized by Fourier transform infrared spectrometry, differential scanning calorimetry, X-ray powder diffraction, and scanning electron microscopy. The result revealed that the graphene oxide was absolutely exfoliated and covalent linked GO/PF composite was obtained. The thermal stability of PF is remarkably improved by modification with GO.