Electrospun web may possibly be widely applied to protective garments or specialty textiles due to its high level of protection as well as comfort. Of particular interest in this study is to develop waterproof-breathable fabric by applying electrospun web of polyurethane directly onto the substrate fabric. The optimal electrospinning condition was examined with regards to the concentration, applied voltage and tip-to-collector distance. Solvent-electospinning of polyurethane was performed at the optimum condition, using N,N-dimethylacetamide as solvent. The thickness of 0.02 mm of electrospun web was applied onto the polyester/nylon blended fabric. For comparison, the polyester/nylon fabrics were coated with 0.02 mm thickness of polyurethane resin membranes adopting four different conditions. The electrospun PU web/fabric was compared to resin coated fabrics in terms of water-proof and breathable properties. The electrospun web applied fabric showed higher air permeability, vapor transmission, and thermal insulation properties than resin coated fabrics, which can be translated as greater comfort sensation of electrospun applied fabrics. However, water resistance value of electrospun web applied fabric did not reach that of resin coated fabrics.