Poisons and poisonous weapons in armed conflict, especially chemical warfare agents (CWAs), pose serious threats to global security. Porous materials have recently been regarded as promising candidates to defend personnel in a CWA-contaminated environment, but challenges remain for integrating these materials into protective garments without sacrificing the intrinsic flexibility of fibers. Here, we report a rigid-flexible coupling hypercross-linking methodology to create flexible sponge-like nanofibers featuring hierarchical radial gradient porous nanoarchitectures, in which the inner structure is a mesoporous multichambered network, and the outer structure is a dense domain with a microporous network structure. Experimental and computational evidence supports the contention that sponge nanofibers with distinctive pore topology and robust bendability can be designed by manipulating the flexibility of building blocks. The resulting heterogeneous nanofibers exhibit integrated properties of spatially selective superstructures, abundant micropores, interconnected mesopores, a high surface area (579 m2 g-1), remarkable flexibility, and exceptional CWA affinity, which are extraordinarily effective for adsorptive performance (498 mg g-1). The successful synthesis of these materials might inspire the development of chemical protective materials in an efficient, self-standing, and structurally adaptive form.