We designed and synthesized novel star poly(N-isopropylacrylamide) (star-PNIPAm) and star PNIPAm with cyclodextrin (CD) end groups (star-PNIPAm-CD) by atom transfer radical polymerization (ATRP) In the synthesis, beta CD core with 21 initiation sites, heptakis[2 3,6-tri-O-(2 chloropropionyl)] beta-cyclodextrin (21Cl beta CD) was first synthesized by the reaction of beta-CD with 2 chloropropionyl chloride (CPC) Then, 21-arm star PNIPAm (PDI = 1 03) was synthesized by ATRP of N-isopropylacrylamide (NIPAm) initiated via 21Cl-beta CD Finally, a star-PNIPAm-CD (PDI = 1 02) was synthesized by ATRP of a monovinyl beta CD (GMA EDA beta CD) initiated via star-PNIPAm The obtained star-PNIPAm and star-PNIPAm-CD were characterized by means of SEC/MALLS NMR, IR, and DSC By using 8-anilino-1 naphthalenesulfonic acid ammonium salt hydrate (ANS) 1 adamantanamine hydrochloride (ADA NH3Cl), and ibuprofen sodium salt (ibuprofen Na) as guest molecules, thermal sensitivity and inclusion behaviors of the star polymers were investigated by fluorescence spectrophotometer and DLS It is found that the star polymers can combine both thermal sensitivity of PNIPAm and inclusion behavior of beta-CD Interestingly, the star polymers can self-assembly to form nanosized aggregates in aqueous solution above their LCSTs The self assembly behavior shows molecular recognition capability And formation and dissociation of the nanosized aggregation can change reversibly by changing temperature above and below the LCST