Composite bilayer nanofibrous membranes of polylactic acid (PLA)/polyurethane (PU) were prepared by electrospinning, which can be used as wound dressing scaffolds for controlled drug loading and release. Besides, doxorubicine (DOX) and paeonolum, which had been successfully electrospun into nanofibers, were employed as the model of antitumor drugs to electrospin with in the nanofibrous membranes. The properties of the membranes were characterized by scanning electron microscope (SEM), atomic force microscopy (AFM), Fourier transform infrared spectrum (FTIR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Furthermore, the releasing profiles of drug from the PLA/PU electrospun nanofibrous membrane were investigated by UV-visible spectrophotometer. It was shown that the drugs on the scaffolds were released when the composite nanofibrous membranes were decomposing, which was related to the molecular weight of polymers, the mass ratio of CS to PEO, the total concentration of polymers and the pH value of solution. Therefore, possible mechanisms of controlled drug release were anticipated. A unique bilayer nanofibrous membrane was prepared in this study.