Biobased resources are proposed as next‐generation materials for advanced application. Among them, silk fibroin, a protein‐based material generally obtained from Bombyx mori cocoons, is considered to play an increasing role in the development of a more sustainable generation of devices. In this review, the silk fibroin molecular structure and its original properties are presented, together with a wide overview of the available modifications and processing methods to reach custom structural and functional variations.

Melt electrowriting (MEW) is an emerging additive manufacturing (AM) technology that enables the precise deposition of continuous polymeric microfibers, allowing for the creation of high‐resolution constructs. In recent years, MEW has undergone a revolution, with the introduction of active properties or additional functionalities through novel polymer processing strategies, the incorporation of functional fillers, postprocessing, or the combination with other techniques. While extensively explored in biomedical applications, MEW's potential in other fields remains untapped. Thus, this review explores MEW's characteristics from a materials science perspective, emphasizing the diverse range of materials and composites processed by this technique and their current and potential applications. Additionally, the prospects offered by postprinting processing techniques are explored, together with the synergy achieved by combining melt electrowriting with other manufacturing methods. By highlighting the untapped potentials of MEW, this review aims to inspire research groups across various fields to leverage this technology for innovative endeavors.