Disulfide/Hydrogen Bond Synergized Dynamic TADF Polymers With Intrinsic Stretchability and Self‐Healing Property for High‐Efficiency Electroluminescence

ABSTRACT Self‐healing is critical for flexible semiconductor reliability and lifetime. Herein, self‐healing intrinsically stretchable thermally activated delayed fluorescence (TADF) polymers are developed through internal plasticization. Two polymer families, blue‐emissive CzBN‐C(X)‐P(Y) and blue–green‐emissive 5CzBN‐C(X)‐P(Y), were synthesized by covalently incorporating TADF emitters, long‐alkyl plasticizing segments, and dual healing motifs, dynamic disulfide bonds and polyurethane hydrogen bonds, into one backbone. This design preserves efficient TADF excited‐state characteristics, enhances segmental mobility, and enables stress dissipation and interfacial reconstruction through a synergistic physical–chemical dynamic network. The films show photoluminescence quantum yield (PLQYs) up to 78%, 65% elongation at break, and structural/optoelectronic recovery within 15 min at 50°C. Blue–green devices reach 18.56% external quantum efficiency (EQE), while red‐dye‐doped white devices achieve 19.17% EQE and 11218 cd m −2 luminance. As MR‐TADF sensitizers, these polymers enable efficient narrowband stretchable self‐healing blue films for the first time, affording devices with 14.35% EQE and 32 nm full width at half maximum (FWHM). Devices retain emission under a 2 mm bending radius and approximately 80% of initial performance after ten fracture–healing cycles. This study realizes, for the first time at the molecular level, the integration of internal‐plasticization‐enabled stretchability, dual dynamic self‐healing, and efficient TADF emission, providing a new molecular design strategy and material platform for next‐generation deformable organic optoelectronic devices with high stability and long operational lifetimes.