The ultrafine fibers of poly(ε-caprolactone) (PCL) composited with different Polyvinyl Pyrrolidone (PVP) content were successfully prepared by electrospinning method. The morphology, hydrophilicity and in vitro degradation behavior of samples were characterized by Scanning Electron Microscopy (SEM), water contact angle and weight loss rate. Pore size and distribution on the fibers changed with the increase of PVP content. The hydrophilicity of PCL membrane was improved by addition of PVP. When the content of PVP was 25% and 50%, the water contact angle approached zero. The degradation was essentially a dissolution process of PVP on the first 7days. Since large specific surface, high porosity and different crystallinity, percent degradation loss of electrospun fiber membranes were about 1 to 12 times higher than that of cast films.