Quick transfer of sweat from skin to atmosphere and dryness of textile inner surface are of scientific and commercial interests. However, creating a balance between these two parameters remains a serious challenge. In this work, electrospun double-layered membranes constructed of poly(vinylidene fluoride) fibrous layer (as inner hydrophobic layer) and nylon6 nanofibrous layer (as outer hydrophilic layer) are produced. Once a thin hydrophobic layer is considered, the enhanced water pulling mechanism is balanced out by increased wetted area in the inner surface. This is handled through selecting an optimum thickness for the inner layer. The designed double-layered membrane is a promising candidate for developing modern breathable textiles with enhanced moisture management properties such as sportswear.