Long-subchain hyperbranched polystyrene (lsc-hp PSt) with uniform subchain length was obtained through copper-catalyzed azide-alkyne cycloaddition click chemistry from seesaw macromonomer of PSt having one alkynyl group anchored at the chain centre and two azido group attached to both chain ends [alkynyl-(PSt-N3)2]. After precipitation fraction, different portions of lsc-hp PSt having narrow overall molecular weight distribution were obtained for further grafting with alkynyl-capped poly(N-isopropylacrylamide) (alkynyl-PNIPAM), which was obtained via single-electron transfer living radical polymerization of NIPAM with propargyl 2-bromoisobutyrate as the initiator and grafted onto the peripheral azido groups of lsc-hp PSt via click chemistry. Thus, amphiphilic lsc-hp PSt grafted with PNIPAM chains (lsc-hp PSt-g-PNIPAM) was obtained and would have star-like conformation in tetrahydrofuran (THF). By replacing THF with water, lsc-hp PSt-g-PNIPAM was dissolved at molecular level in aqueous solution due to the hydrophilicity of PNIPAM and exhibited thermal induced shrinkage of PNIPAM arms. The water-insoluble lsc-hp PSt would collapse densely and could be served as a reservoir to absorb hydrophobic chemicals in aqueous solution. The influence of overall molecular weight of lsc-hp PSt on the absorption of pyrene was studied. (c) 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013, 51, 2142-2149