In this work, we report the fabrication and cell affinity studies of the poly(vinyl alcohol) (PVA)/hyaluronic acid (HA) cross-linked nanofibers via electrospinning and post cross-linking. FT-IR and TGA analysis demonstrate that HA is not influenced by acid environment such as HCl vapor during cross-linking, and well incorporated into PVA nanofibers. Swelling behavior and cell adhesion of the PVA/HA hydrogel nanofibers are investigated and compared with pure PVA hydrogel nanofibers. It is expected that the nanofibrous PVA/HA hydrogel fibers could be a promising scaffold for cell culture and tissue engineering applications