PCL/PVP blend membrane was prepared by casting solution method. Scanning electron microscopy (SEM), diffraction scanning calorimetry (DSC), and X-ray diffraction (XRD) techniques were employed to characterize membrane structure and morphology. Moreover, the hydrophilicity, mechanical property and biodegradability of membranes were investigated. Due to introducing PVP, the crystallinity and mechanical property of PCL altered to some extent. The hydrophilicity of the blend membrane improved remarkably with increasing PVP content, which was expressed by the contact angle declining and the rate of water absorption increasing. Lipase accelerated the degradation rate of PCL/PVP membrane.