Developing novel and efficient adsorption materials to solve water pollution is a very challenging task for the sake of environmental protection and human health. Herein, an ultra-light and porous 3D nanofiber aerogels (NFA) has been prepared by freezing casting technology and cross-linking with epichlorohydrin(ECH) via short polyacrylonitrile (PAN)/polyetherimide (PEI) nanofibers, which features high mechanical stability and good mass transfer performance. Moreover, experiments show that the adsorption capacities of 3D nanofiber aerogels (NFA) for Cu(II), Cr(VI), As(V) and anionic dye methyl orange (MO) reach 242.71 mg/g, 214.14 mg/g, 258.36 mg/g and 183.06 mg/g, respectively. Importantly, the adsorbent still maintains considerable adsorption efficiency after seven adsorption-regeneration cycles.