Autonomous Polymer Frameworks for Sustainable Tissue‐Interfaced Plastic Bioelectronics

This review focuses on plastic bioelectronic systems integrated with autonomous polymer frameworks (auto‐POFs) and summarizes recent progress in this field. It provides an in‐depth analysis of the design strategies and operational mechanisms of auto‐POFs, highlighting their pivotal role in enhancing the sustainability and interfacial adaptability of bioelectronic systems, and outlines the future direction for the development of next‐generation wearable and implantable systems. Abstract Recent advancements in polymer science have enabled the development of plastic bioelectronics, providing soft, stretchable, and tissue‐conformable technologies for continuous health monitoring, diagnostics, and therapeutic interventions. Unlike conventional silicon‐based electronics that often exhibit mechanical mismatches with biological tissues, plastic bioelectronic systems leverage intrinsically soft and mechanically compliant organic and polymer materials to achieve enhanced conformability. This reduces interfacial stress and enables high‐fidelity signal acquisition from dynamic tissue interfaces. However, the low mechanical modulus that enables their unique advantages also makes these systems susceptible to mechanical damage, weak adhesion, and functional degradation under physiological conditions. To overcome these limitations, emerging research focuses on integrating autonomous polymer frameworks (auto‐POFs)–engineered materials that endow the polymer matrix with self‐adhesion, self‐protection, self‐healing, self‐degradation, and self‐sensing capabilities. These features enable real‐time responsiveness to stimuli and extend device lifespan without external intervention. This review provides a comprehensive overview of recent progress in auto‐POF‐based systems, including their material design strategies, functional mechanisms, and roles in enhancing the reliability and adaptability of sustainable, wearable, and implantable tissue‐interfaced plastic bioelectronics. By highlighting key material innovations and device architectures, the path is outlined toward next‐generation biomedical platforms capable of autonomous and sustainable operation in dynamic biological environments. This review focuses on plastic bioelectronic systems integrated with autonomous polymer frameworks (auto-POFs) and summarizes recent progress in this field. It provides an in-depth analysis of the design strategies and operational mechanisms of auto-POFs, highlighting their pivotal role in enhancing the sustainability and interfacial adaptability of bioelectronic systems, and outlines the future direction for the development of next-generation wearable and implantable systems. Abstract Recent advancements in polymer science have enabled the development of plastic bioelectronics, providing soft, stretchable, and tissue-conformable technologies for continuous health monitoring, diagnostics, and therapeutic interventions. Unlike conventional silicon-based electronics that often exhibit mechanical mismatches with biological tissues, plastic bioelectronic systems leverage intrinsically soft and mechanically compliant organic and polymer materials to achieve enhanced conformability. This reduces interfacial stress and enables high-fidelity signal acquisition from dynamic tissue interfaces. However, the low mechanical modulus that enables their unique advantages also makes these systems susceptible to mechanical damage, weak adhesion, and functional degradation under physiological conditions. To overcome these limitations, emerging research focuses on integrating autonomous polymer frameworks (auto-POFs)–engineered materials that endow the polymer matrix with self-adhesion, self-protection, self-healing, self-degradation, and self-sensing capabilities. These features enable real-time responsiveness to stimuli and extend device lifespan without external intervention. This review provides a comprehensive overview of recent progress in auto-POF-based systems, including their material design strategies, functional mechanisms, and roles in enhancing the reliability and adaptability of sustainable, wearable, and implantable tissue-interfaced plastic bioelectronics. By highlighting key material innovations and device architectures, the path is outlined toward next-generation biomedical platforms capable of autonomous and sustainable operation in dynamic biological environments. Advanced Science, EarlyView.