Saimeng Li, Yimin Yang, Yurim Bae, Yuxiang Li, Han Young Woo, Yanhou Geng, Long Ye
ABSTRACT The accelerated adoption of thermoplastic elastomers (TPEs) is driving a critical shift toward wearable electronics and highly durable energy technologies that are both mechanically durable and high‐performing. This feature‐article systematically examines the rapidly expanding role of TPEs across key device platforms, specifically organic photovoltaics and thermoelectrics, and explores how TPEs enable their synergistic integration with other crucial functionalities such as light‐emitting diodes, thin‐film transistors, photodetectors, and electrochemical transistors within advanced flexible energy systems. The integration of TPEs in various devices enables unprecedented improvements in both mechanical robustness and electronic functionality critical for sustained energy performance. The distinctive two‐phase microstructure of TPEs, which combines dynamically reversible physical crosslinks with flexible soft segments, enables tunable mechanical behavior and superior interfacial compatibility. This architecture allows TPEs to serve multiple critical functions, as flexible substrates, encapsulation layers, adhesion promoters, and toughening agents, significantly improving stretchability, structural adaptability, and performance retention under mechanical deformation for energy conversion and storage applications. By critically analyzing recent breakthroughs, this review formulates essential design guidelines and persistent challenges for optimizing TPE‐incorporated devices. Collectively, this work underscores the transformative and practical potential of TPEs in realizing advanced, intelligent, and highly durable energy‐harvesting and power‐supply systems for next‐generation wearable applications.