<p>The advances of biobased triboelectric materials have further boosted the sustainable development of triboelectric nanogenerators. Especially biobased polyamides have attracted increasing attention thanks to their outstanding mechanical properties, wear resistance and sustainability. However, the unavoidable thermal deformation of common biobased polyamides restricts their application as a triboelectric material under high temperatures. It is necessary to develop polyamides with superior thermal stability and further expand their application scenarios. In this work, a semi-aromatic biobased high-performance polyamide (BH-PA) and its composites were integrated into TENGs to serve at high temperatures. Owing to the outstanding thermal stability of BH-PA composites (HDT &gt; 200°C, <i>T</i>_m&gt; 310°C, and <i>T</i>_{d, 5%}&gt; 400°C), the resultant TENGs can achieve stable triboelectric output at 200°C, and even perform better than at 25°C. Additionally, triboelectric spectroscopy associated with the dielectric properties of polyamide composites is innovatively utilized as an analysis technique to detect the content of fillers. Overall, this work not only provides a high-performance composite for the construction of TENGs in extreme conditions, but also promotes the application of triboelectric spectroscopy in the analytical testing field.</p>