Abstract: Photonic crystal (PC) is a structure formed by the periodic arrangement of dielectric materials. Due to its distinct photoregulatory features, it has drawn significant attention in the realm of optics and photonics. From the structure, mechanism, material, and functional application, people have carried out in-depth research and continuous development. Because of their large specific surface area and customizable three-dimensional structure, photonic crystal fibers (PCFs) in particular provide new opportunities for the development of detecting sensing, smart wearables, photoelectric transmission, and other sectors. In this paper, the structure and color mechanism of PC, basic materials, preparation methods, and applications of PCFs are reviewed. The contribution of electrostatic spinning technology in the field of PCFs is highlighted, as are the functional applications of PCFs in textile printing and dyeing, intelligent response, sensing detection, and hydrophobic regulation are discussed. Finally, the problems in macro preparation and practical production application of PCFs are pointed out, and the possible research focus and direction in the future have prospected.