Nereis Jaw‐Inspired Pretreatment‐Free Direct Metallization on Pristine Polyimide Films for Flexible Electronics

Surface metallization of polyimide (PI) films is essential for constructing conductive electrodes and interconnects in flexible electronics, directly determining device integration and reliability. However, the high inertness and low surface energy of PI necessitate complex pretreatment in conventional vacuum deposition, incurring high costs and substrate damage, while wet etching faces environmental burdens and poor compatibility, both failing to meet large‐scale manufacturing demands. Inspired by the stable coordination of histidine in Nereis jaws, a coordination‐directed molecular design strategy is proposed. By introducing nitrogen‐containing heterocyclic units into PI molecular chains, intrinsic metal anchoring sites are constructed, enabling direct film metallization without destructive adhesion‐promoting surface pretreatments. This process integrates with photolithography, printing, and direct writing for cross‐scale controllable metallization, fabricating planar wiring and vertical interconnect access (VIA) structures for 3D high‐density integration. The metallized PI films with azaindole‐bearing diamine moieties achieve the highest 5B‐grade adhesion and exhibit excellent environmental stability, tolerating repeated bending, high‐temperature exposure, and ultrasonic impact. Commercial PI surface metallization can be achieved with minimal functional monomers and is directly compatible with electronic soldering and device integration. This strategy overcomes the trade‐off between interfacial adhesion and substrate integrity, providing a viable pathway for scalable flexible electronics manufacturing.