Abstract
Polymeric semiconductors have rapidly evolved from early conductive polymers, such as polyacetylene, to high-performance donor-acceptor copolymers, offering a unique combination of mechanical flexibility, solution processability, and tunable optoelectronic properties. These advancements have positioned polymeric semiconductors as versatile materials for next-generation electronics, including wearable, stretchable, and bio-integrated devices, IoT systems, and soft robotics. In this review, we systematically present the fundamental principles of polymeric semiconductors, including electronic structure, charge transport mechanisms, molecular packing, and solid-state morphology, and elucidate how these factors collectively govern device performance. We further discuss recent advances in synthesis strategies, thin-film processing techniques, molecular doping, and interface engineering, emphasizing their critical roles in improving operational stability, charge-carrier mobility, and energy efficiency. Key applications-such as organic photovoltaics, field-effect transistors, neuromorphic devices, and memristors-are analyzed, with a focus on the intricate structure-property-performance relationships that dictate functionality. Finally, we highlight emerging directions and scientific innovations, including sustainable and degradable polymers, hybrid and two-dimensional polymer systems, and novel strategies to enhance device stability and performance. By integrating fundamental polymer science with device engineering, this review provides a comprehensive, structured, and forward-looking perspective, identifying knowledge gaps and offering insights to guide future breakthroughs and the rational design of high-performance, multifunctional, and environmentally responsible polymeric electronic devices.