A novel monofunctional β -cyclodextrin monomer is synthesized via copper(I)-catalyzed azide/ alkyne click reaction. By free radical polymerization, cyclodextrin-containing polyelectrolytes can be obtained as an intriguing polymeric host for smart supramolecular assembling systems. By inclusion complexation of adamantyl carboxylate as a model guest, pseudo-betaine structures with reversible UCST behavior are obtained. Furthermore, the complex stability constants are determined by isothermal titration calorimetry at different temperatures.a Both the authors contributed equally to this work. solution temperature (UCST) in aqueous solutions. [20][21][22] Yui and co-workers [ 23 ] reported that inclusion complexes of β -cyclodextrin-conjugated poly( ε -lysine) with 3-trimethylsilylpropionic acid form supramolecular assemblies, which showed a rapid response on the UCST behavior by a small change of pH or temperature. [ 23 ] Furthermore, reversible self-association was observed in certain polyzwitterionic hydrogels that display an UCST. At high temperature, the dipolar interactions broke to yield isolated polymer chains that were completely solvated. [ 24 ] The fi rst synthesis of a zwitterionic polymer was described in 1957. [ 25 ] Polyzwitterions and polybetaines belong to a special class of polyampholytes, where each monomer carries both the positive and negative charges. [25][26][27][28][29] An extended inquiry through literature reveals that only covalent betaine structures are described. Until now, there has been no investigation on the formation of betaine structures via supramolecular host/guest interactions. In this study, we thus describe the synthesis and characterization of a novel β -CD containing polyelectrolyte. Furthermore, the properties and the ability to form betaine structures due to supramolecular host/ guest interactions are investigated.