In the contemporary era, marked by escalating environmental pollution and energy scarcities, the advancement of microscale, flexible, and wearable optoelectronic devices has become a primary area of research focus. Polymer nanofibers, notable for their extensive specific surface area, superior conductivity, and high electron mobility, have risen to prominence within this domain. These fibers now play a pivotal role in a variety of optoelectronic applications, including light-emitting devices, photodetectors, photovoltaics, transistors, and generators, as well as in energy storage devices like supercapacitors. This review provides a comprehensive examination of the synthesis of polymer nanofibers and their applications in optoelectronics, while also discussing future developmental prospects.