© 2016 The Royal Society of Chemistry. Novel nanocomposite sorbents of superparamagnetic iron oxide nanoparticles (SPION) supported onto electrospun polyacrylonitrile nanofibers were synthesized by a simple and scalable method. The influence of both nanofiber size and SPION loading on As(v) adsorption capacity was studied and optimization was conducted. A maximum uptake capacity of 32.5 mmol As(v) per gram SPION in batch mode tests using an extremely low loading of only 2.9 mg of SPION per gram of adsorbent was achieved. This represents a remarkable improvement of 36 times compared with SPION in suspension. The optimal material was tested in continuous flow operation mode, reaching an adsorption capacity of 851.7 mg As(v) per gram of adsorbent at pH 3.8. It is also demonstrated that the new adsorbents can retain high performance when tested under real conditions using polluted wastewater from a lixiviation dump containing a large amount of competing anions (Cl- and F-) and interfering cations (K+, Na+, Mg2+, and Ca2+). Furthermore, there was no release of nanoparticles observed during the operation and the spent porous material can be compressed, generating a small amount of solid waste that can be easily treated or stored.