Gold nanoparticles (AuNPs) were attached to the surface of alumina particles by an in-situ immobilizing method. SEM and XPS analysis showed that the coverage of alumina particles by AuNPs increased as the amount of alumina decreased; AuNPs onto alumina particles by the conventional colloidal deposition method were also prepared, whose TEM showed that the coverage of AuNPs was evidently smaller than that in the case of modified colloidal deposition method,although the AuNPs were spread almost uniformly over the surface of alumina particles. Au-immobilized alumina particles were subsequently utilized as the catalysts for direct amination of benzene with NH3H2O as an aminating agent and H2O2 as an oxidant under mild conditions. The reaction conditions were optimized: when catalyst amount was 2.0 g, reaction temperature was 50 °C, NH3H2O amount was 60 mL, H2O2 amount was 30 mL, and reaction time is 2 h, Au-immobilized alumina particles showed the highest aniline yield (1.96 mg) for 25 mL benzene.