A three-dimensional biomimetic electrospun scaffold was prepared from a nanohydroxyapatite/ polymer blend in the present study. Viscosity of n-HA/PEA compound solution determined by PEA concentration and additives of n-HA was investigated while other parameters were fixed in the electrospinning process. The fiber diameter increased with the increasing viscosity of solution. 20wt% n-HA in the composite ultrafine fibrous scaffold was proved to be a preferable ratio. The n-HA/PEA scaffold was characterized by XRD, SEM and EDX. The fibrous electrospun scaffold, which is made up of ultrafine fibers with average diameter 400±50 nm and well-interconnected pores, was characterized with high surface–to-volume ratio, which is conducive to cell and tissue growth. A comparatively uniform distribution of n-HA crystals in a single fiber even in the whole scaffold was confirmed by EDX. The biocompatibility of the composite was investigated by culturing osteobalsts on the scaffold. Good cell adhesion and proliferation manner was observed on the fibrous scaffold by SEM and MTT assay. It could be expected that the electrospun HA/PEA composite scaffold would be a potential biomimetic extracellular matrix biomaterial for bone tissue engineering.