It has been a major challenge to treat osteoporotic bone defects with irregular shapes. Although bioactive glass offers an attractive material for bone regeneration, its inherent brittleness has greatly limited its scope of application. Herein, we report the fabrication of bioactive glass (SiO2-CaO) nanofibers with excellent flexibility to even allow for 180° bending. The bioactive glass nanofibers could be further assembled into 3D fibrous scaffolds with chitosan serving as the linkers. The scaffolds constructed from an assembly of 85SiO2-15CaO nanofibers and chitosan (85SiO2-15CaO NF/CS) possessed significantly better mechanical properties when benchmarked against both 75SiO2-25CaO nanofiber- and chitosan-based scaffolds. Moreover, the 85SiO2-15CaO NF/CS scaffolds exhibited an elastic behavior, with full recovery from 80% compression and good fatigue resistance over 1000 cycles of compression under water. Upon implantation, the elastic fibrous scaffolds were able to deform and fit irregularly shaped bone defects, followed by a self-deploying behavior to achieve a perfect match with the cavities. When applied to the repair of an osteoporotic calvarial defect in a rat model, the 85SiO2-15CaO NF/CS scaffolds showed substantial promotion of bone regrowth and vascularization. This new class of 3D fibrous scaffold provides a promising advancement in engineering smart materials for complex bone repair.