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As triboelectric nanogenerator (TENG) technology continue to evolve, its application in harsh environments has increasingly captivated the interest of researchers. However, the current research on heat-resistant triboelectric materials remains predominantly focused on the development of tribo-negative materials, with scant attention given to their equally crucial tribo-positive counterparts. In this study, the tribo-positive polyimide (PI) material with enhanced tribo-positivity is developed by integrating amide groups with electron-donating effects into the molecular chain. Furthermore, the TENG devices based on this series of tribo-positive PI materials have demonstrated an open-circuit voltage (<i>V_OC</i>) of 242 V, a short-circuit current (<i>I_SC</i>) of 8.13 μA, and a transferred charge (<i>Q_SC</i>) of 117 nC. Notably, these devices also demonstrate the capability to efficiently generate electricity even under elevated temperature conditions. This work not only proposes a potential molecular design strategy for developing high-performance tribo-positive PI materials applicable in TENGs, but also markedly propels the advancement of robust energy-harvesting devices engineered for operation at elevated temperatures.