Triboelectric nanogenerators (TENGs) have garnered significant attention due to their high energy conversion efficiency and extensive application potential in energy harvesting and self-powered devices. Recent advancements in electrospun nanofibers, attributed to their outstanding mechanical properties and tailored surface characteristics, have meant that they can be used as a critical material for enhancing TENGs performance. This review provides a comprehensive overview of the developments in electrospun nanofiber-based TENGs. It begins with an exploration of the fundamental principles behind electrospinning and triboelectricity, followed by a detailed examination of the application and performance of various polymer materials, including poly (vinylidene fluoride) (PVDF), polyamide (PA), thermoplastic polyurethane (TPU), polyacrylonitrile (PAN), and other significant polymers. Furthermore, this review analyzes the influence of diverse structural designs—such as fiber architectures, bionic configurations, and multilayer structures—on the performance of TENGs. Applications across self-powered devices, environmental energy harvesting, and wearable technologies are discussed. The review concludes by highlighting current challenges and outlining future research directions, offering valuable insights for researchers and engineers in the field.