Multilayer Stretchable Electronics: Technological Innovations From Molecular Engineering to Integrated System

Multilayer stretchable electronics with vertically integrated architectures and intrinsic conformability enable system‐level functionality and alleviate the mechanical mismatch between rigid silicon‐based electronics and curvilinear surfaces, holding promise for multimodal sensing, on‐board computing, closed‐loop feedback, and wireless communication under large‐scale deformation. However, the intricate mechanical‐electrical design required for heterogeneous vertical integration introduces coupled challenges in molecular engineering, interfacial reliability, structural topology, and scalable manufacturing. This review presents a synergistic technological framework for multilayer stretchable electronics from molecular engineering to system integration, based on a comprehensive summary of advances in material development, topological design, manufacturing technologies, and application expansion. In particular, key interface‐engineering strategies are examined, including the regulation of thermodynamic compatibility, the design of dynamic self‐healing interfaces, the optimization of interlayer mechano‐electrical coupling, and manufacturing approaches for heterogeneous integration. Finally, unresolved challenges and future directions are discussed, including sustainable materials, advanced manufacturing techniques, and artificial intelligence integration. This review aims to provide a systematic theoretical and methodological reference for next‐generation high‐performance multilayer stretchable electronic systems.