Over the past few decades, significant progress in piezo-/triboelectric nanogenerators (PTEGs) has led to the development of cutting-edge wearable technologies. Nanofibers with good designability, controllable morphologies, large specific areas, and unique physicochemical properties provide a promising platform for PTEGs for various advanced applications. However, the further development of nanofiber-based PTEGs is limited by technical difficulties, ranging from materials design to device integration. Herein, the current developments in PTEGs based on electrospun nanofibers are systematically reviewed. This review begins with the mechanisms of PTEGs and the advantages of nanofibers and nanodevices, including high breathability, waterproofness, scalability, and thermal–moisture comfort. In terms of materials and structural design, novel electroactive nanofibers and structure assemblies based on 1D micro/nanostructures, 2D bionic structures, and 3D multilayered structures are discussed. Subsequently, nanofibrous PTEGs in applications such as energy harvesters, personalized medicine, personal protective equipment, and human–machine interactions are summarized. Nanofiber-based PTEGs still face many challenges such as energy efficiency, material durability, device stability, and device integration. Finally, the research gap between research and practical applications of PTEGs is discussed, and emerging trends are proposed, providing some ideas for the development of intelligent wearables.