In this article, we report the synthesis of unique mesoporous Au-loaded Fe2O3nanoparticle assemblies (Au/Fe2O3-NPAs) through a surfactant-assisted aggregating assembly method. The resulting network structure, which composed of small Au nanocrystals (ca. 5 nm) finely dispersed on surface of Fe2O3 NPs (ca. 6–7 nm), possesses a 3D open-pore structure with a BET surface area of 123 m2g-1 and uniform mesopores (∼4.5 nm). Au/Fe2O3-NPAs showed high catalytic activity and chemical stability for the selective transformation of nitroaromatic compounds into the corresponding amines, using 1,1,3,3-tetramethyl disiloxane as reducing agent at ambient conditions.