Covalent fixed multicyclic polystyrene conformers were synthesized from inconvertible polystyrene conformers based on p-tert-butylthiacalix[4]arene by azidation and subsequent click coupling. Selective 1D NOESY analyses confirmed that the spatial structures of star polystyrene precursors and multicyclic polystyrenes were preserved during the azidation and click coupling processes. The conformation of star polymers affected degree of decrease in the hydrodynamic volume after cyclization but had little effect on glass transition behavior. The rigid core of star polymer increased the T-g but in the case of multicyclic polymer, this influence of core structure was reduced. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 4020-4026