Amorphous monodisperse spheres of amino-functionalized zirconia (ZrO2) were prepared by the co-condensation of zirconium tetrabutoxide as the precursor of ZrO2 in the presence of aminopropyltriethoxy silane (APS) as the source of terminal amino groups. The resultant amino functional groups possess lone-pair electrons that can be coordinated with Ag seed colloid to immobilize the Ag seeds on the surface of ZrO2. Ag seeds tethered on the surface of the amino-functionalized ZrO2 served as nucleation sites for the growth of Ag nanoshell overlayer via the reduction of AgNO3 by polyvinylpyrrolidone (PVP), thereby affording core–shell structure ZrO2@Ag composite. The microstructure and chemical state of the as-prepared ZrO2@Ag composite were characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy, and its catalytic activity towards the hydrogenation reduction of Rhodamine B (RhB) and 4-nitrophenol (4-NP), two of common organic dye, was evaluated by ultraviolet–visible spectrophotometry. The results indicate that the uniformly distributed Ag nanoparticles with average size of 10nm are strongly attached to ZrO2 surface. Besides, the as-prepared ZrO2@Ag composite exhibits excellent catalytic performance for the hydrogenation reduction of RhB and 4-NP.