This study presents a dual-layer artificial dura mater, a hierarchically structured fibrous membrane composed of poly(p-dioxanone) (PPDO) and bioactive glass (BG), fabricated using electrospinning and melt-casting techniques. Designed to address the challenges of dura mater repair, the membrane features a dense outer PPDO layer for mechanical resilience and an electrospun inner layer embedded with BG to enable controlled ion release, promoting tissue regeneration and angiogenesis. We evaluated the fibrous membrane's surface morphology, mechanical properties, hydrophilicity, and in vitro degradation, demonstrating that increasing BG content enhances hydrophilicity, reduces crystallinity, and modulates degradation kinetics. In vitro assays using L929 fibroblasts and human umbilical vein endothelial cells reveal that the PPDO/BG membrane not only supports cell adhesion and proliferation but also fosters a pro-angiogenic environment through the controlled release of bioactive silicon ions. In vivo implantation in a rat dura mater defect model further validates its therapeutic potential, showing reduced adhesion, improved tissue integration, and enhanced vascularization, with the PBD-3 variant exhibiting superior performance due to its optimized BG composition. The synergistic effects of bioactive ion release, mechanical stability, and biocompatibility establish the PPDO/BG membrane as a highly promising dura mater substitute, offering a bioengineered solution for neurosurgical applications aimed at functional tissue regeneration.