Well-defined H-shaped pentablock copolymers composed of poly(N-isopropylacrylamide) (PNIPAM), poly(N,N-dimethylaminoethylacrylamide) (PDMAEMA), and poly(ethylene glycol) (PEG) with the chain architecture of (A/B)-b-C-b-(A/B) were synthesized by the combination of single-electron-transfer living radical polymerization, atom-transfer radical polymerization, and click chemistry. Single-electron-transfer living radical polymerization of NIPAM using a, x azide-capped PEG macroinitiator resulted in PNIPAM-b-PEG-b-PNIPAM with azide groups at the block joints. Atom-transfer radical polymerization of DMAEMA initiated by propargyl 2-chloropropionate gave out alpha-capped alkyne-PDMAEMA. The H-shaped copolymers were finally obtained by the click reaction between PNIPAM-b-PEG-b-PNIPAM and alkyne-PDMAEMA. These copolymers were used to prepare stable colloidal gold nanoparticles (GNPs) in aqueous solution without any external reducing agent. The formation of GNPs was affected by the length of PDMAEMA block, the feed ratio of the copolymer to HAuCl4, and the pH value. The surface plasmon absorbance of these obtained GNPs also exhibited pH and thermal dependence because of the existence of PNIAPM and PDAMEMA blocks. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5018-5029, 2010