Polyurethane (PU) was synthesized by one-shot process and the PU nanofiber was prepared by electrospinning. In this study, electrospun PU multi-membranes were prepared with various coating thickness ratio of base resin to top resin, where the base resin contains melamine curing agent and acid catalyst and the top resin contains water-repellent agent of fluoro-carbon compounds. The PU nanofiber multi-membranes were analyzed by field-emission scanning electron microscopy, differential scanning calorimeter, breathability, tensile strenth, air permeability and water resistance. The results showed that the PU multi-membrane provided excellent waterproof and moisture permeability.