Visualizing color changes upon mechanical force in elastomers is attractive to understand stress transfer and failure mechanisms, which is valuable for applications ranging from tamper-proof packaging to structural integrity monitoring. Herein, we synthesize mechanochromic polyurethane films with an optimum stretchability (5500% strain) and a strongest toughness (324 MJ m−3) by using the components of bis-functionalized rhodamine, Diels–Alder (DA) adduct, 2-hydroxyethyl disulfide (HEDS), polyethylene glycol, triethanolamine and hexamethylene diisocyanate via condensation polymerization. The additions of HEDS and DA moieties enhance the healing efficiency up to 87% after 24 h of curing induced by disulfide bond exchange and Diels–Alder and retro-Diels–Alder reactions. The polyurethane film exhibits a green emission (450–500 nm) before stretching, but it shows an orange-red emission (588 nm) by force stretching because of the open form of the rhodamine moieties. A high shape recovery of 90.9% and reversible mechano-fluorescence switching by heating (immersed in 60 °C hot water) after structural deformations make it useful for shape memory and soft robotic applications. Finally, a high dielectric permittivity (160 at 1 Hz) and a good capacitance value (0.28 nF cm−2 at 1 Hz) of the film exhibit its potential applications as a flexible capacitor for energy storage in modern flexible devices.