LAUSR

To address the challenge of realizing multifunctional polymers simultaneously exhibiting high strength and high toughness through molecular engineering, ultrastrong and supertough shape‐memory poly(urea‐urethane) (PUU) is fabricated by regulating: i) the reversible cross‐links composed of rigid units and multiple hydrogen bonds, and ii) the molecular weight of soft segments. The optimal material exhibits an unparalleled strength of 84.2 MPa at a large elongation at a break of 925.6%, a superior toughness of 322.8 MJ m−3, and remarkable fatigue resistance without fracture. The repeated stretching of this material induces an irreversible deformation, which, however, can be rapidly recovered by heating. Moreover, all samples are capable of temporary shape fixation at −40 °C (recovering the original shape at 30 °C) and exhibit blue fluorescence when excited at the optimum wavelength, which is ascribed to clusterization‐triggered emission (CTE) due to the formation of microphase‐separation structures. Thus, the adopted approach provides a solution to a long‐standing problem and paves the way to the realization of intrinsically luminescent shape‐memory materials exhibiting both ultrahigh strength and ultrahigh toughness.