A simple and versatile synthetic methodology to silver metal nanoparticles that utilizes 3,5-dihydroxybenzyl alcohol-based dendrimers as templates and does not necessitate the addition of any external reducing agent is reported. An evaluation of the role of addition rate of the silver acetate solution, and the dendrimer to silver acetate molar ratio, as well as the dendritic effect on nanoparticle growth, suggests that the size of these metal nanoparticles can be controlled by simple variations of these parameters. A probe of the mechanism of the nanoparticle formation and growth indicates that the terminal hydroxyl groups of the dendrimers play a major role in metal ion isolation and reduction, in addition to providing stabilization to the growing metal particles. These silver metal nanoparticles are highly active catalysts for the selective reduction of chloronitrobenzenes to chloroanilines. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4482-4493, 2009