Electrospinning is a common technology to construct tissue engineering scaffolds for bone regeneration. However, pure electrospun scaffolds do not enrich seed cells or promote their osteogenic differentiation. Biological functionalization of tissue engineering scaffolds is currently a hot research topic. Therefore, in this study, the bone marrow-derived mesenchymal cells (BM-MSC)-specific affinity peptide E7 and a bone morphogenic protein 2 (BMP-2) mimetic peptide were concomitantly conjugated onto the surface of an electrospun scaffold to construct a functional PEB scaffold. Characterization of PEB scaffolds revealed that both E7 and BMP2 mimetic peptides were successfully conjugated onto the surface of electrospun scaffolds. With regard to biological activity, the PEB scaffold could synchronously promote adhesion and osteogenic differentiation of BM-MSC as a result of the co-delivery of E7 and BMP-2 mimetic peptides, which proved superior compared with the other three scaffolds. Consequently, the PEB scaffold offers a new concept for the construction of bone tissue engineering scaffolds.