In this work, three-dimensional (3-D) porous scaffolds based on poly(epsilon-caprolactone)-poly(ethylene glycol)-poly(epsilon-caprolactone) (PCL-PEG-PCL, PCEC) and nano-hydroxyapatite (n-HA) were prepared by the electrospinning method. The physical-chemical properties of the composite membranes were investigated by Fourier transform infrared spectroscopy, X-ray diffraction, differential scanning calorimetry, water contact angle measurements, and a tensile test. Morphological study using scanning electron microscopy showed that the average fiber diameter decreased from about 1 mu m (for pure PCEC membrane) to 0.6 mu m (containing 30% HA) with the increase of HA contents. At high content (> 10%), agglomeration of HA can be observed on the surfaces of composite membranes fibers, which decreased the tensile strength and elongation rate of the samples. In vitro osteoblast cell culture demonstrated the electrospun n-HA/PCEC composite scaffolds could provide a suitable environment for cell attachment, and MTT results revealed the scaffolds had good biocompatibility and nontoxicity. The results indicated that such n-HA/PCEC fibrous membranes might have potential applications in tissue engineering field.