A protocol for the preparation of novel triblock copolymers comprising a polyrotaxane center block and outer blocks of poly(N-isopropylacrylamide) (PNIPAAm) as bulky stoppers was developed, in which N-isopropylacrylamide was allowed to telomerize in the presence of polypseudorotaxanes made from the self-assembly of thiol end-capped PEG with a varying amount of alpha-CDs under UV irradiation in aqueous solution. The molecular structure of the resulting copolymers was characterized in detail by H-1 NMR, FTIR, XRD, TG and DSC analyses. It was demonstrated that the PNIPAAm blocks are successfully attached to the two terminals of the polypseudorotaxanes and each block having the minimum 7 NIPAAm units seems long and bulky enough to efficiently impede the dethreading of alpha-CDs from the PEG axle to give rise to the triblock polyrotaxane-containing copolymers. (c) 2006 Elsevier Ltd. All rights reserved.