Polymer particles with dendrimer@SiO2-Ag hierarchical shell were prepared, and their application in the catalytic column for the reduction of 4-nitrophenol (4-NP) was also investigated. The PS microspheres with the carboxyl group were used as the supports for the immobilization of dendrimer@SiO2-Ag shell. The polyamidoamine (PAMAM) dendrimer was grafted on the surface of PS microsphere through repetitive Michael addition reaction of methyl acrylate (MA) and amidation of the obtained esters with a large excess of ethylenediamine (EDA) successively. The silver nanoparticles formed inside the PAMAM shell. Then, the silver nanoparticles, which were used as center of nucleation, were coated with SiO2 shell through improved Stober method. Moreover, the more silver nanoparticles were dispersed on the surface of SiO2 shell. The contents of silver element were measured using inductively coupled plasma (ICP-MS). The obtained PS@PAMAM@SiO2-Ag nanoparticles were packed in stainless steel column, which has been used effectively for the catalytic reduction of 4-NP. Under column pressures, the rigid SiO2 shell plays a better role in immobilization of silver nanoparticles than the soft PAMAM shell. This technique for packing catalytic nanoparticles in column improves the efficiency of application with metal catalysts as well as reduces the tedious separation processes in catalytic reaction. (C) 2011 Elsevier Inc. All rights reserved.