Creating adsorptive materials for fast, efficient, and high-throughput adsorption and purification of proteins is critical to meet the great demands for highly purified proteins, yet has proven to be an highly challenging task. Here, we report that the cross-linked and highly carboxylated poly(vinyl alcohol) (PVA) nanofibrous membranes were fabricated by the combination of electrospinning and in-situ graft polymerization of PVA and maleic anhydride (MAH) under mild conditions. Taking advantages of the large surface area available for proteins binding, highly tortuous porous structure, and robust mechanical properties, the resultant PVA/MAH nanofibrous membranes exhibited integrated adsorption performance towards lysozyme involving superior adsorption capacity of 177 mg g -1 , fast adsorption equilibrium within 4 h, good selectivity, and good reversibility. Moreover, the saturation dynamic adsorption amount towards lysozyme reached 159 mg g -1 under 750 Pa driven solely by gravity, which was conformance to specify requirements for high adsorption capacity under relatively low pressure-drops. Furthermore, the adsorption performance towards proteins mixture was analyzed by sodium dodecyl sulphate-polyacrylamide gel electrophoresis and the resultant PVA/MAH nanofibrous membranes remained excellent stability under depyrogenation conditions. The successful fabrication of such fascinating nanofibrous materials by using this simple and intriguing approach may provide new insights into the design and development of adsorptive materials for purification proteins with superior adsorption performance.