Abstract: The properties of materials play a significant role in triboelectric nanogenerators (TENGs). Advanced triboelectric materials for TENGs have attracted tremendous attention because of their superior advantages (e.g., high specific surface area, high porosity, and customizable macro structure). These advanced materials can be extensively applied in numerous fields, including energy harvester, wearable electronics, filtration, and self-powered sensors. Hence, designing triboelectric materials as advanced functional materials is important for the development of TENGs. Herein, the structural modification methods based on electrospinning to improve the triboelectric properties and the latest research progress in this kind of TENGs are systematically summarized. Preparation methods and design trends of nanofibers, microspheres, hierarchical structures and doping nanomaterials are highlighted. The factors influencing the formation and properties of triboelectric materials are considered. Furthermore, the latest progress on the applications of TENGs is systematically elaborated. Finally, the challenges in the development of triboelectric materials are discussed, thereby guiding researchers in the large-scale application of TENGs.