Ordered mesoporous silver nanoparticle/carbon composites have been produced by a “one-pot” synthesis method. They have open mesopores (4.2–5.0nm), large specific surface areas (465–584m2g−1) and high pore volumes (0.29–0.50cm3g−1) and contain stable, confined but accessible Ag nanoparticles. As a result, they show high performance in catalytic reduction of 4-nitrophenol (4-NP). The mesostructure and particle size as a function of Ag content were studied and correlated with the catalytic activity. The ordered mesoporous carbon framework and highly dispersed Ag nanoparticles make the material a novel system for effective contacting with the reactants and catalysis of the reaction.