Effective membranes that have the osteogneic potential and the ability to recruit osteoblast precursor cells challenged guided bone regeneration (GBR). Herein, we engineered multifunctional nanofiber membranes by using eletrospun poly(ε-caprolactone) (PCL) and silk fibroin (SF), incorporated with octacalcium phosphate (OCP) and BMSCs-affine peptide (E7) to form the PCL/SF/OCP/E7 (PSOE) nanofiber, wherein the E7 peptide enhances the enrichment of BMSCs, and OCP as osteogenesis promoter. The composite membranes enhance the recruitment and biomineralization processes essential for bone regeneration. Notably, the dual functionality of BMSC recruitment and osteoinduction provides a "recruitment-osteoinduction" strategy that significantly improves bone repair. In vitro analyses confirmed that the PSOE nanofibers have superior hydrophilicity and biocompatibility, and significantly upregulated the expression of osteogenic genes in mesenchymal stem cells, thereby facilitating osteogenic differentiation. In vivo studies using a rat tibial defect model revealed that PSOE nanofibers promoted bone repair within 8 weeks, as validated by micro-CT and histological evaluations. This study highlights the PSOE nanofiber's potential as a promising synthetic periosteum substitute for effective bone regeneration.