Acid-base bifunctional catalyst is of particularly interest, but also has great challenges in synthesis and applications. In this study, the acid-base bifunctional graphene oxide hybrids was obtained by the modification of graphene oxide (GO) through silylation reaction and radical addition reaction. The obtained bifunctional hybrids displayed high acid and base catalytic activities towards a typical one-pot acid-base reaction sequence called Deacetalization–Nitroaldol reaction.