Structural design is of great importance to the performance of photocatalysts in environmental remediation. Therefore, micro/nanofibrous morphology and nanoporous local structures have been found to be beneficial to improve the photocatalytic activity. In this investigation, we report the design and fabrication of flexible and thermal stable nanoporous SiO2-TiO2 composite fibers as efficient photocatalysts. Combining electrospinning and modified Stober techniques, core-shell and mesoporous SiO2 fibers with high flexibility were fabricated and employed as the scaffold for supporting TiO2 nanoparticles. A nanoporous shell of TiO2 nanoparticles was then muffled over the SiO2 fibers to form core@dual-shell SiO2-TiO2 composite fibers with hierarchically porous structure, which were conveniently patterned into a nonwoven, recyclable film. This nonwoven film exhibits better photocatalytic activity for Rhodamine B degradation under UV irradiation compared with some other TiO2-based materials reported in recent years.