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Fe3O4/P(GMA-DVB)/PAMAM/Au microspheres are fabricated to research the catalytic performances to 4-nitrophenol. In the preparation process, Fe3O4 microspheres act as magnetic cores, PAMAM dendrimers growing up on the surface of P(GMA-DVB) polymer work as carriers, and Au nanoparticles serve as catalytic materials. The stability of the prepared microspheres is evaluated by successively catalytic experiments to measure the conversion of 4-nitrophenol, and catalytic efficiency can still maintain up to 78.7% after ten cycles. Moreover, the effects of major factors including the concentration of the prepared microspheres and the temperature of reaction system on the conversion of 4-nitrophenol are also investigated in detail. The manuscript reveals that 4-nitrophenol can be almost converted to 4-aminophenol within 7 min at 45 °C in the case of using 1.0 g/L Fe3O4/P(GMA-DVB)/PAMAM/Au microspheres. Such excellent catalytic properties are ascribed to the optimum structure of the prepared microspheres, which favors the sufficient contact between Au nanoparticles and 4-nitrophenol. The results and strategies exhibited here provide insight into the preparation of sophisticated structures of catalysts to treat wastewater. [ABSTRACT FROM AUTHOR]