Two kinds of amphiphilic comb-like copolymer, i.e., poly(epichlorohydrine)-g-poly(methyl methacrylate) (PECH-g-PMMA) and poly(epichlorohydrine)-g-poly(butyl methacrylate) (PECH-g-PBMA) were synthesized via atom transfer radical polymerization (ATRP) using directly initiating the chlorine atoms of PECH macroinitiator. The amphiphilic comb-like copolymers were used as a template film for the in situ growth of silver nanoparticles from AgCF(3)SO(3) precursor using NaBH(4). UV-visible spectroscopy and transmission electron microscopy (TEM) images indicated that (1) Ag nanoparticles were selectively confined in the comb-like polymer films persisting microphase-separated morphology and (2) Ag nanoparticles (47 nm) formed in PECH-g-PBMA were smaller than those in PECH-g-PMMA (6-11 nm). This represents that the longer hydrophobic side chains in a comb-like copolymer is more effective in controlling the formation of metal nanoparticles. (C) 2009 Elsevier B.V. All rights reserved.