Silver nanoparticles (Ag NPs) were prepared via in situ reduction of silver nitrate (AgNO3) using polymeric micelles as nanoreactors without any additional reductant. The micelles were constructed from the amphiphilic star-shaped copolymer composed of poly(epsilon-caprolactone) (PCL) segment, 2-(dimethylamino) ethyl methacrylate (DMAEMA or DMA) units and oligo(ethylene glycol) monomethyl ether methacrylate (OEGMA or OEG) units. The Ag NPs stabilized by those star-shaped copolymers were characterized using UV-vis spectrum, DLS, TEM and FTIR. It confirmed that PDMAEMA exhibited the reducing property unless pH was above 7. The Ag NPs were sphere-like with a diameter of 10-20 nm, which was independent of the architecture of the copolymer and AgNO3 concentration. Furthermore, the catalytic activity of these Ag NPs was investigated by monitoring the reduction of p-nitrophenol (4-NP) by NaBH4. The result showed that the Ag NPs formed by coordination reduction can be effectively applied in catalytic reaction. (C) 2011 Elsevier B. V. All rights reserved.