Silver nanoparticles stabilized by means of poly-(6-N,N-dimethyl-propylenediamino)-(6-deoxy)-beta-cyclodextrin were synthesized, characterized by different techniques (UV-vis spectroscopy, Dynamic Light Scattering, High Resolution Transmission Electron Microscopy, Fourier-transform IR Spectroscopy) and used as catalysts for the reduction of various nitrobenzene derivatives with sodium borohydride. The nanocomposites obtained appear to have an organized structure, with a metal core surrounded by a layer-structured coating shell. Kinetic data, rationalized in terms of a modified Langmuir-Hinshelwood model, evidenced a non-linear dependence of the reaction rate on the concentration of the catalyst. This was explained on the grounds of the catalytic activity of differently covered catalyst areas. Careful analysis of kinetic data, in particular the effect of the para substituent on the nitroarene structure and the trends of the induction period observed at the beginning of the reaction, provided with interesting insights on the reaction course, and brought us to critically reconsider several mechanistic ideas reported in previous literature. (C) 2015 Elsevier B.V. All rights reserved.