To develop waterproof breathable materials for diverse consumer applications, we used electrospinning to fabricate layered fabric systems with varying composite structures. Specifically, we developed layered fabric structures based on electrospun nanofiber webs with different levels of nanofiber web density, as well as different substrates and layer structures, and then examined the breathability and waterproofness of the material. The breathability and waterproofness of the layered fabric systems were compared with those of traditional waterproof breathable fabrics, including densely woven fabric, microporous membrane laminated fabric, and hydrophilic nonporous polyurethane coated fabric. Different breathability and barrier performance levels were achieved by varying the layer structure and substrates in the electrospun nanofiber web layered fabric systems. The uniformity of the nanofiber web and lamination process also affected the barrier and comfort performances. The comparison of waterproofness and breathability performances between the new materials and the traditional waterproof breathable materials revealed that the layered structures based on electrospun nanofiber webs provide a higher level of resistance to water penetration than densely woven fabrics and a higher degree of moisture vapor and air permeability than microporous membrane laminates and coated fabrics, with a proper selection of layer structure, substrate fabric, and lamination process.