Superfine multifunctional micro/nanoscale fibrous materials with high surface area and ordered structure have attracted intensive attention for widespread applications in recent years. Microfluidic spinning technology (MST) has emerged as a powerful and versatile platform because of its various advantages such as high surface‐area‐to‐volume ratio, effective heat transfer, and enhanced reaction rate. The resultant well‐defined micro/nanoscale fibers exhibit controllable compositions, advanced structures, and new physical/chemical properties. The latest developments and achievements in microfluidic spun fiber materials are summarized in terms of the underlying preparation principles, geometric configurations, and functionalization. Variously architected structures and shapes by MST, including cylindrical, grooved, flat, anisotropic, hollow, core–shell, Janus, heterogeneous, helical, and knotted fibers, are emphasized. In particular, fiber‐spinning chemistry in MST for achieving functionalization of fiber materials by in situ chemical reactions inside fibers is introduced. Additionally, the applications of the fabricated functional fibers are highlighted in sensors, microactuators, photoelectric devices, flexible electronics, tissue engineering, drug delivery, and water collection. Finally, recent progress, challenges, and future perspectives are discussed.