AbstractPerylene‐terminated star elastomers (PSE) containing the diblock copolymers of polystyrene (PS) and polyisoprene (PI) segments were designed and synthesized by anionic polymerization. The PSE exhibits good fluorescence performances in solution, self‐assembled aggregates, and solid state. Different supramolecular self‐assemblies in tetrahydrofuran (THF) solution based on the π−π stacking of perylene and interactions in PS can be observed from nanofibers to twisted multi‐nanoropes. Moreover, the twisted nanoropes under ultrasonic can transform spontaneously into nanorings in the stationary state, and reversibly switch between twisted nanoropes and nanorings via the manipulation of ultrasonic force. The terminating methods will offer considerable scope for the design and synthesis of new star elastomers. Meanwhile, a new insight into π−π stacking and interactions is provided for understanding multistep and cooperative self‐assembly in supramolecular self‐assembly.