To develop a series of novel acidproof and breathable fabric, electrospun fluorinated polyurethane/polyurethane and pitch nanofibers were directly deposited on polyester/cotton blended fabric. The layered and interpenetrated structured membranes were built to study the effects of different structures on the acidproof and breathable performances. The acidproof and breathable mechanism of different structured composite fabrics had been evaluated via emission scanning electron microscope, X-ray photoelectron spectroscopy, contact angle, porosity, pore size, comfort and mechanical test, respectively. The results showed that the layered structured composite fabric had advantages in acidproof property, i.e. the acid (H2SO4, 80%) contact angle was 130° due to the low surface energy caused by the high fluorine content (36.96%). Meanwhile, such structured composite fabric provided double protection, which made the acid-resistance pressure to reach a high value of 1050 Pa, while the interpenetrated structured composite fabric showed superior comfort and mechanical properties. Due to the high porosity (88.01%), the water vapor transport rate and air permeability were 7554.14 g/m2·24h and 46.33 mm/s, respectively. Due to the relative slip of fluorinated polyurethane/polyurethane fibers was restricted, the tensile strength and bursting strength of interpenetrated one was 1315 N and 795 N, which were higher than layered one.