In this study, a bifunctional graphene oxide material (GO-AEP-UDP) with a general acid, the ureidopropyl (UDP) group, and a general base, the 3-[2-(2-aminoethylamino)ethylamino]-propyl (AEP) group, was synthesized by silylanization of graphene oxide (GO) with organoalkoxysilane precursors. Characterization of the obtained GO-AEP-UDP was carried out by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and zeta potential measurements. Systematic studies demonstrated that GO-AEP-UDP has superior catalytic performance in the classic Henry reaction of 4-nitrobenzaldehyde with nitromethane. It was found that the relative concentration and spatial arrangement of cooperative functional groups were very important factors in the synergistic catalysis. 2014 This journal is © the Partner Organisations.