Polymers with high surface electric insulation capability are greatly demanded in various electrical devices operating in vacuum ambient. Low secondary electron emission (SEE) is favorable to mitigate vacuum flashover by inhibiting the SEE avalanche across the surface. Although numerous approaches, esp. the surface modifications, promote the flashover strength of the insulator, a facile yet cost-effective modification strategy of a highquality and scalable flexible insulator remains a formidable challenge. Herein, a facile ion-exchange technique is implemented to fabricate a nanoscale polyimide/chromic oxide (PI/Cr2O3) nanocomposite coating comprising hundreds of organic/inorganic interfaces securely adhered to a flexible PI substrate, which features ultralow secondary electron emission yields (SEEY). The low emissivity is achieved by introducing weakly emissive Cr2O3 nanoparticles as well as interfacial traps within the nanocomposite layer, which outperforms the existing and modified polymers. The PI/Cr2O3 shows a remarkable increase in flashover strength while keeping sufficient mechanical durability. The proposed surface engineering strategy is convenient and scalable, bringing up new insight into industrial applications.