Nano-hydroxyapatite (n-HA)/poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone) (PCL-PEG-PCL, PCEC) composite membranes were prepared by solvent casting and evaporation method. The structure and properties of the membranes were investigated by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), water contact angle measurements, in vitro hydrolytic degradation, mechanical test, and cell culture. The effect of n-HA content on physical-chemical properties of the n-HA/PCEC composite membranes was studied. The results showed that the shape and size of micropores of the composite membranes changed with n-HA content increased; the tensile strength decreased with the increase of n-HA content. The osteoblast cell was cultured on the membranes, good cell attachment and growth manner were observed after postseeding for 1 day. MTT assays showed that the n-HA/PCEC membranes had no negative effect on the cell viability and proliferation. These results suggested that the obtained n-HA/PCEC composite membranes in this study might have prospective applications in tissue engineering field.