Multistimuli-responsive polymers containing mechanophoric motifs are highlighted as promising mechano-luminescent materials upon stretching via optical fluorescence signals. Herein, we report a distinct ratiometric force-induced fluorescence changes from green-emissive napthalimide stopper (donor) embedded in polyrotaxane (PR) cross-linkers to red-emissive rhodamine mechanophore (acceptor) incorporated in polyurethane (PU) backbones. The utilization of PR (1 wt %) can significantly enhance both toughness and stretchability in our targeted PU elastomers, where the mechanical work is largely dissipated by the ring-sliding motion and pulley effects of PR crosslinkers during stretching. Therefore, the simple soft robotic behavior with ultrafast shape memory and reversible ratiometric mechanochromic fluorescence switching by heating (60 °C) in PR-based PU films provide a distinctive strategy for the construction of molecular machines in the high-performance elastomers, which also offer pathways for practical applications of stimuli-responsive polymers in highly stretchable artificial muscles featuring both outstanding pulley effects on enhanced mechanical properties and novel signal variations of mechanochromic fluorescence simultaneously.