Self‐healing soft electronic material composition is crucial to sustain the device long‐term durability. The fabrication of self‐healing soft electronics exposed to high moisture environment is a significant challenge that has yet to be fully achieved. This paper presents the novel concept of a water‐assisted room‐temperature autonomous self‐healing mechanism based on synergistically dynamic covalent Schiff‐based imine bonds with hydrogen bonds. The supramolecular water‐assisted self‐healing polymer (WASHP) films possess rapid self‐healing kinetic behavior and high stretchability due to a reversible dissociation–association process. In comparison with the pristine room‐temperature self‐healing polymer, the WASHP demonstrates favorable mechanical performance at room temperature and a short self‐healing time of 1 h; furthermore, it achieves a tensile strain of 9050%, self‐healing efficiency of 95%, and toughness of 144.2 MJ m⁻³. As a proof of concept, a versatile WASHP‐based light‐emitting touch‐responsive device (WASHP‐LETD) and perovskite quantum dot (PeQD)‐based white LED backlight are designed. The WASHP‐LETD has favorable mechanical deformation performance under pressure, bending, and strain, whereas the WASHP‐PeQDs exhibit outstanding long‐term stability even over a period exceeding one year in a boiling water environment. This paper provides a mechanically robust approach for producing eco‐friendly, economical, and waterproof e‐skin device components.

Silver nanowire (AgNW) networks have attracted considerable attention as transparent electrodes for emerging flexible optoelectronics. However, the transference of such networks onto diverse arbitrary substrates with high conductivity remains a challenge because of the possibility of detaching and sliding occurring at the interface. Therefore, we developed a water-assisted transfer printing method for the fabrication and transfer of an AgNW–polydimethylsiloxane (PDMS) electrode. This innovative approach exhibits a robust ability for thin film transfer onto arbitrary substrates and has highly controlled and nondestructive characteristics. The obtained electrodes exhibited a high ratio of DC conductivity to optical conductivity of 200, a low sheet resistance of 9 Ω sq⁻¹ at 82%, tensile strain (0% to 50%), and flexibility (bending radius of less than 2 mm) without significant loss of conductivity compared with devices fabricated through conventional methods. Furthermore, we demonstrated a novel textile-based flexible light-emitting electrochemical cell (PLEC) based on the stretchable AgNW–PDMS electrode and buckling concept, thereby realizing highly stretchable PLECs with excellent performance and mechanical robustness. The luminance intensity of the strained device was optimized to 58 cd m⁻² at 7 V under 10% linear strain without damaging the electroluminescence properties. Notably, this effective and practical transfer method provides a way to develop electronic nanowire devices with unique configurations and high performances.