Electromechanical Network Constructed From Adaptive Olefin Nodes and Regionally Conductive sp 2 Carbon for High‐Performance Piezoresistive Sensors

Polyimide (PI) aerogels have demonstrated excellent thermal stability and mechanical performance in flexible piezoresistive sensors. However, simultaneously achieving high compressive resistance, superelasticity, and stable, repeatable electrical responses without modifying the conventional PI monomer structure remains a significant challenge. This limitation mainly originates from the isotropic entanglement of polyimide chains, which hinders the effective coupling between mechanically induced deformation and the long‐range transport of charge carriers. To address this issue, alkyne functional units were introduced into the PI molecular backbone and subsequently converted, via high‐temperature chemical reactions, into alkene chain structures with sp 2 hybridization characteristics, thereby constructing a PI aerogel with a stably cross‐linked, chain‐supported network. The resulting alkene chains form a load‐bearing cross‐linked framework that enables adaptive stress distribution to maintain structural stability, while their sp 2 ‐hybridized backbone establishes locally continuous conductive pathways, ensuring reliable transmission of pressure signals. The further incorporation of carbon nanotubes (CNTs) significantly enhances conductive network connectivity and structural synergistic effects, enabling the simultaneous optimization of mechanical performance and electrical stability. Notably, crosslinked polyimide/commercial polyimide/carbon nanotube (Co/C‐PI‐CNTs) aerogels，prepared via structural regulation, with a strain of 50%, exhibited a high stress recovery rate of 94% after 10 000 extremely long stable compression cycles, which was about 27% higher than that of comparable aerogels (74%) under identical conditions. This work broadens the perspective for designing force‐electric transmission networks at the molecular scale in the piezoresistive sensors.