Triboelectric nanogenerators (TENGs) offer promising green energy solutions for portable microelectronics in the Internet of Everything era. However, their practical applications are limited by low electrical output and stability in harsh environments. This study introduces an innovative antagonistic strategy to enhance TENG performance and stability using thermo-stable polyimide with customizable porous structures (ip-PI). By employing antagonistic solubility, we create ip-PI using chloroform as a solvent for PI and acetone as a solvent for the Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) template, whereas they both act as nonsolvents for their respective counterparts. Additionally, microbeads-patterned chitosan (mb-CS) is rationally designed and fabricated as morphologically and electrically antagonistic counter surfaces for ip-PI. The resulting antagonist-inspired TENG (AI-TENG) constructed from ip-PI and mb-CS achieves a remarkable average power density of 4 W·m−2, presenting an outstanding 200-fold increase in power compared to TENG made from unstructured flat surfaces. Furthermore, the ip-PI demonstrates excellent temperature resistance, enabling the TENG to operate at extremely high temperatures up to 250 °C, with promising durability of over 10,000 contact-separation cycles. Applications include self-powered machinery condition monitoring sensors and a wireless communication fire forest pre-warning system, showcasing significant advancements in flexible, high-performance TENGs suitable for industrial use in extreme environments.