In this study, primary and tertiary amine bifunctional graphene oxide (GO-NH2-NEt2) was prepared by silylanization of graphene oxide (GO) with amine-terminal silanes. The obtained GO-NH2-NEt2 was characterized by infrared spectrum (FTIR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). Systematic studies demonstrated the GO-NH2-NEt2 had excellent catalytic activities and 100% selectivity in the classic trans-β-nitrostyrene forming reaction.