In this study, phosphotungstic acid immobilized on amine-grafted graphene oxide (GOAP) was prepared successfully by silylanization and electrostatic interaction. The obtained GOAP was characterized by Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), high-resolution transmission electron microscopy (HRTEM), zeta potential measurements, and X-ray photoelectron spectroscopy (XPS). Systematic studies demonstrated that GOAP had excellent catalytic activities and robustness in the one-pot tandem deacetalization-nitroaldol reaction. The key role of the acid/base ratio in the catalytic performance of this bifunctional catalyst was also revealed by preliminary kinetic studies. This bifunctional catalyst might find promising applications in green chemistry, as it can not only reduce costs and waste by saving separation/purification steps and solvents/reagents, but also increase the yield by avoiding the separation of intermediate products.