Electrospun nanofibers have been widely used in triboelectric nanogenerators (TENGs) due to their customizable micro-nano structures, high specific surface area, and porosity. It is of great significance to summarize the recent advances of electrospun nanofibers for the development of TENGs. Herein, the development and characteristics of electrospun nanofiber triboelectric materials were systematically introduced, and the applications of TENGs prepared by electrospun nanofibers in different fields were emphatically described. Electrospun nanofiber materials were broadly utilized in TENGs owing to their unique advantages, such as convenient preparation, superior electrical properties, and expansibility. Hence, it has promising application prospects to prepare electrospun nanofibers triboelectric materials for TENGs in energy harvesting, self-powered sensors, and wearable electronics, which will be expanded to intelligent packaging, printing and other fields in the future.