The blend fibrous membranes with the different mass ratio of silk fibroin (SF) powder to polyurethane (PU) were fabricated by electrospinning. The structure, morphology, mechanical properties, and surface wettabilities of the blend fibrous membrane are characterized by field-emission scanning electron microscope, Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetry, dynamic mechanical thermal analysis, tensile testing, and contact angle measurements. The results show that the SF was uniformly distributed in the blend fibers. The mass ratio of SF to PU played an important role in influencing the structure and morphology of the blend fibers, and the optimum mass ratio was 5/5. With the increase in SF content in fibers, the fraction of SF in the surface of the SF/PU blend fibers and the crystallinity degree of PU increased, and the molecular orientation of PU along the fiber axis took place. The SF content regulated the hydrophilicity property of the membrane. The thermal stability and the dynamic storage modulus of the fibrous membrane decreased, and the phase separation between soft and hard segments of PU increased. Similarly, the stress at peak and Young's modulus of the fibrous membrane decreased gradually; the strain at peak first increased and then decreased. POLYM. ENG. SCI., 52:20252032, 2012. (c) 2012 Society of Plastics Engineers