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.

While melt electrowriting (MEW) can result in complex microstructures, research demonstrating such fabrication with active materials is limited. Herein, magnetoresponsive poly(ε‐caprolactone) (PCL) inks containing up to 10 wt% of iron‐oxide (Fe₃O₄) nanoparticles are used to produce fiber with diameters of 9.2 ± 0.6 µm in ordered microstructures when processed by MEW. Introducing the Fe₃O₄ nanoparticles has a minimal overall effect on printing quality compared to pure PCL under similar conditions. The magnetic response of Fe₃O₄ containing fibers allows magnetic actuation, which is one of the first steps to control movement in such structures. Printed samples show different magnetic responses that can be controlled by the micro‐ and macro‐structure design, the nanoparticle concentration, and multi‐material design. The potential of MEW to print active magnetic complex micro‐ and macro‐structures for 4D printing designs is demonstrated, in which active properties can be further tailored with magnetoresponsive fillers with varying characteristics and by changing MEW fiber diameters.