In this work, novel nanofibrous membranes with waterproof and breathable (W&B) performance were successfully fabricated by the combination of electrospinning and surface modification technology. This fibrous membranes consisted of polyurethane (PU), NaCl, and fluoroalkylsilane (FAS). Firstly, The fibrous construction and porous structure of fibrous membranes were regulated by tuning the NaCl concentrations in PU solutions. Then, the obtained PU/NaCl fibrous membranes were further modified with fluoroalkylsilane (FAS) to improve hydrophobic property. The synergistic effect of porous structure and hydrophobicity on waterproof and breathable performance was investigated. Furthermore, the mechanical property of fibrous membranes was deeply analysed on the basis of macromolecule orientation and adhesive structure. Benefiting from the optimized porous structure and hydrophobic modification, the resultant fibrous membranes exhibited excellent waterproof (hydrostatic pressure of 1261 Mbar), breathable (water vapor transmission (WVT) rate of 9.06 kg m(-2) d(-1) and air permeability of 4.8 mm s(-1)) performance, as well as high tensile strength (breakage stress of 10.4 MPa), suggesting a promising candidate for various applications, especially in protective clothing. (C) 2018 Elsevier B.V. All rights reserved.