The synthesis and NMR-spectroscopical characterization of the topological arrangements of new side-chain polyrotaxanes (3a) bearing about 80% of peracetylated cyclodextrins in the side-chains of a functionalized poly(ether sulfone) is described. The characterizations have been conducted in relation to a similar model compound bearing no cyclodextrins (3b). The results strongly indicate that the cyclodextrins are uniformly located on the side chains, with the bigger opening over the aromatic anilide components of the barrier group. The glass transition temperature (T-g) of the polyrotaxane 3a is in the region of 143 degrees C, which is significantly higher than that of the model polymer 3b having a value of 111 degrees C.