Abstract: The rodlike nano-hydroxyapatite (nHA) which synthesized by hydrothermal route induced the ringopening polymerization of ε-caprolactone and nHAPCL composites were obtained. Polycaprolactone (PCL), the mixed material (nHA/PCL) and nHAPCL were used to prepare membranes respectively via electrospinning. The structure, mechanical properties and thermostability of the three electrospun membranes were characterized by FT-IR, DSC, SEM, TGA and tensile testing machine. The results of the FT-IR and DSC showed that PCL in nHAPCL membrane had better crystalline ability than the other two membranes. The results of tests showed that nHA-PCL membrane had better mechanical properties and thermostability than other two membranes. The complete decomposition temperature of nHAPCL membrane was 420 °C. The tensile strength and the breaking elongation of nHA-PCL membrane were 28.2 MPa and 55.6%, respectively. The SEM results showed that the fibers diameter of the three membranes were lower than 500 nm, but the fiber surface of nHA/PCL electrospun membrane became rough. After immersion in SBF for 4 d, there was much more calcium phosphate on the surface of nHAPCL electrospun membrane comparing with PCL and nHA/PCL electrospun membranes. The boneforming ability of nHA-PCL compound material was good.