In this study, several nanofibrous polyurethane (PU) webs were electrospun (ES) by changing different effective parameters (e.g., polymeric concentration, voltage, feed flow, etc.). The physical-chemical properties of the webs (i.e., average fiber diameters, thickness, areal density, porosity, contact angle, waterproofness, air permeability (AP), water vapor transmittance, and aerosol filtration) were studied based on the standard test methods. A commercially available waterproof breathable (WPB) fabric was used as a reference for benchmarking. The beads-free webs with an average fiber diameter as small as 200 nm were achieved from electrospinning of 10 wt % PU in N,N-dimethylformamide, at feed rate of 0.5 mL/h, applied voltage of 25 kV, and tip-to-collector distance of 15 cm. By optimizing the electrospinning parameters, a web with a high level of waterproofness, high AP, and high water vapor transmission rate (WVTR) was obtained. In addition, the selected ES membrane showed very promising aerosol filtration efficiency with complete removal of particles larger than 0.5 mm, and 94% reduction in the concentration of smaller particles. We found a linear empirical equation for the estimation of AP and WVTR based on the average pore size diameter, the membrane thickness, and the porosity with very high regression coefficients (R 2 > 0.97).