Interactions between bone marrow-derived hematopoietic stem cells (BM-HSCs) and their local microenvironment are an integral part of signaling control of BM-HSCs migration, proliferation and differentiation. We hypothesized that both substrate topographical and biochemical cues promote BM-HSCs adhesive behaviors, which are crucial for BM-HSCs' homing, self-renewal and lineage commitment within their microenvironment. We employed electrospinning technique to fabricate nanofiber scaffolds (NFS) with poly(dl-lactide-co-glycolide) blended with collagen I. NFS was further coated with E-selectin, a critical adhesive biomolecule. Capture efficiency study showed that blended NFS, after coated with E-selectin, significantly increased cell capture percentage from 23.40% to 67.41% within 30 min and from 29.44% to 70.19% within 60 min of incubation at room temperature. This study highlights the potential of using a biomimetic scaffold to design a site-specific niche-like unit for facilitating proliferation or differentiation functions of BM-HSCs.