<p>Developing high-performance TENG based on electrospun nanomaterials is one key to maximize the value as a sustainable green energy technology. Here, a performance-enhanced TENG is constructed by using electrospun TPU/Tb(BA)₃phen/PVP nanofiber membrane and PVDF/PVP nanofiber membrane as two friction layers. A “dual-enhancement strategy” is proposed and implemented: a lot of micro contact points are created by utilizing the nanofiber membrane network structure to greatly increase the effective contact area and significantly enhance the frictional electrification effect. Meanwhile, a multitude of triboelectric charge capture sites are obtained via Tb(BA)₃phen-TPU/PVP two-phase interface that is established by doping functional filler of Tb(BA)₃phen to reduce charge dissipation and increase the accumulation of frictional charges. As the content of Tb(BA)₃phen increases from 0 to 15% in TPU/Tb(BA)₃phen/PVP nanofiber membrane, the output performance of TENG gradually increases from 3.3&#xa0;μA, 50&#xa0;V to 10.1&#xa0;μA, 200&#xa0;V. Moreover, electrospun nanofiber membranes are endowed with rich properties, including good flexibility, stretchability, hydrophobicity, and fluorescence. The assembled TENG with high performance and excellent multifunctional integration has great potential in wearable electronic devices and energy harvesting.</p> Graphical abstract <p></p>