This review summarizes the development of stimuli-responsive materials based on the topology transformable polymers from branched to linear. The junction point of the rotaxane components bearing plural polymer chains is the key for the topology transformation which cannot be attained by the fixed junction point formed by the covalent bond. Crown ether-containing macromolecular [2]rotaxane with both ammonium and urethane moieties (M2R) as the stations for the crown ether wheel on the axle polymer chain produces the controllable and movable junction point of the polymer chains via the control of the component interaction, which enables the construction of sophisticated dynamic polymer systems. The rotaxane-linked star polymers with a fixed rotaxane linkage owing to the ammonium/crown ether interaction were synthesized by the introduction of two additional polymer chains to the components of M2R. The star polymers altered their topology to linear by the N-acetylation of the ammonium moiety, which broke the ammonium/crown ether interaction and generated the urethane/crown ether interaction to move the wheel component to the polymer chain terminal, eventually affording the linear polymer. The change in physical property caused by the topology transformation was confirmed in hydrodynamic volume and viscosity, demonstrating an effective way to the development of novel stimuli-responsive materials.