Polymer complex fibers (PCFs) are a novel kind of fiber material processed from polymer complexes that are assembled through noncovalent interactions. These can realize the synergy of functional components and miscibility on the molecular level. The dynamic character of noncovalent interactions endows PCFs with remarkable properties, such as reversibility, stimuli responsiveness, self-healing, and recyclability, enabling them to be applied in multidisciplinary fields. The objective of this article is to provide a review of recent progress in the field of PCFs. The classification based on chain interactions will be first introduced followed by highlights of the fabrication technologies and properties of PCFs. The effects of composition and preparation method on fiber properties are also discussed, with some emphasis on utilizing these for rational design. Finally, we carefully summarize recent advanced applications of PCFs in the fields of energy storage and sensors, water treatment, biomedical materials, artificial actuators, and biomimetic platforms. This review is expected to deepen the comprehension of PCF materials and open new avenues for developing PCFs with tailor-made properties for advanced application.