With the rapid development of the Internet of Things (IoT) and the emergence of 5G, traditional silicon-based electronics no longer fully meet market demands such as nonplanar application scenarios due to mechanical mismatch. This provides unprecedented opportunities for flexible electronics that bypass the physical rigidity through the introduction of flexible materials. In recent decades, biological materials with outstanding biocompatibility and biodegradability, which are considered some of the most promising candidates for next-generation flexible electronics, have received increasing attention, e.g., silk fibroin, cellulose, pectin, chitosan, and melanin. Among them, silk fibroin presents greater superiorities in biocompatibility and biodegradability, and moreover, it also possesses a variety of attractive properties, such as adjustable water solubility, remarkable optical transmittance, high mechanical robustness, light weight, and ease of processing, which are partially or even completely lacking in other biological materials. Therefore, silk fibroin has been widely used as fundamental components for the construction of biocompatible flexible electronics, particularly for wearable and implantable devices. Furthermore, in recent years, more attention has been paid to the investigation of the functional characteristics of silk fibroin, such as the dielectric properties, piezoelectric properties, strong ability to lose electrons, and sensitivity to environmental variables. Here, this paper not only reviews the preparation technologies for various forms of silk fibroin and the recent progress in the use of silk fibroin as a fundamental material but also focuses on the recent advanced works in which silk fibroin serves as functional components. Additionally, the challenges and future development of silk fibroin-based flexible electronics are summarized. (1) This review focuses on silk fibroin serving as active functional components to construct flexible electronics. (2) Recent representative reports on flexible electronic devices that applied silk fibroin as fundamental supporting components are summarized. (3) This review summarizes the current typical silk fibroin-based materials and the corresponding advanced preparation technologies. (4) The current challenges and future development of silk fibroin-based flexible electronic devices are analyzed.