Pyrrolyl-capped poly(N-isopropylacrylamide) macromonomers (Py-PNI-PAM)were prepared through reversible addition-fragmentation-transfer polymerization with benzyl 1-pyrrolylcarbodithioate as chain-transfer agent. Polymerizations of Py-PNIPAM with/without pyrrole using AgNO3 as oxidizing agent and dimethylforamide as solvent resulted in graft copolymers of polypyrrole-graft-poly(N-isopropylacrylamide) (PPy-g-PNIPAM) as well as silver nanoparticles, leading to the formation of PPy-g-PNIPAM/silver nanocomposites. The resulting nanocomposites were soluble in water when the content of PPy was low, and when the molar ratio of Py/Py-PNI-PAM increased to 30, the resulting products became insoluble in water. The resulting nanocomposites had special optical properties because of PPy as well as the temperature-responsible PNIPAM. The chemical structure and composition of nanocomposite were characterized by H-1 nuclear magnetic resonance spectroscopy, gel permeation chromatograms, fourier transform infrared spectroscopy, and X-ray diffraction. Their optical properties were characterized by UV-vis and fluorescence spectroscopy. (c) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6950-6960, 2008