Herein, we developed a bioactive nanofibrous membrane by coating the bioactive glass nanofiber with degradable biopolymers, such as poly(caprolactone) and poly(lactic acid). A thin layer of the biopolymers could be covered on the glass nanofiber through a capillary-driven infiltration of the polymer solution into the small-sized nanofibrous mesh. The biopolymer-coated glass nanofiber showed significantly enhanced mechanical properties while preserving the excellent bioactivity of the glass nanofiber. The produced nanofibrous membrane may be useful as a bioactive substrate for defect-filling and cell-culturing in bone regeneration area.