Hollow multiple-Ag-nanoclustes-C-shell nanostructures containing stabilized Ag nanocluster and hollow C shell were successfully fabricated from well-defined Ag@C core-shell templates via a simultaneous synthesis and assembly strategy. The core-shell Ag@C templates were hydrothermally achieved using glucose and silver nitrate reactants, and the glucose served as mild reducing agent for reducing Ag+ to Ag and as carbon source for generating C shells with active groups, simultaneously. Then the hollow multiple-Ag-nanoclustes-C-shell nanostructures were fabricated by a redox reaction between the Ag@C templates and H2O2 center dot H2O2 played a role of smart etchant in controlling dissolving and oxidizing the initial Ag cores to Ag+ anions. During such transformation process, Ag+ was firstly diffused from Ag core to C shell and then reduced into Ag nanoclusters by the active groups in the C shell. The dispersion, particle size and the arrangement of Ag nanoclusters in the C shell depended heavily on the processing time. The hollow multiple-Ag-nanoclustes-C-shell nanostructures exhibit an excellent catalytic activity and recyclability for the reduction of p-nitrophenol due to their small size, high dispersion, and high number density of the Ag nanoclusters on the C shell. (C) 2015 Elsevier B.V. All rights reserved.