Antibacterial, anti-inflammatory, and pro-angiogenic properties are prerequisites for dressing materials that accelerate the healing process of infected wounds. Herein, we report a magnesium-doped silica bioactive glass (SiO2/MgO) nanofiber membrane prepared by electrospinning. Our results demonstrate that this SiO2/MgO nanofiber membrane has good flexibility and hydrophilicity, which give it intimate contact with wound beds. In vitro assessments illustrate its good cytocompatibility and bioactivity that contribute to its robust cell proliferation and angiogenesis. It shows capacity in modulating the cellular inflammatory response of murine macrophages. In addition, in vitro assays prove its good antibacterial activity against both Gram-positive and Gram-negative strains. In a full-thickness skin defect inoculated with Staphylococcus aureus in mice, it effectively inhibits bacterial infection. Both gene expression and histological/immunohistochemical analyses confirmed the down-regulated pro-inflammatory factors, up-regulated anti-inflammatory factors, and enhanced angiogenesis. Taken together, these desirable properties work in concert to contribute to the rapid healing of infected wounds and make it a good candidate for wound dressing materials.