Functionalized electrospun polymer microfibrous membranes were fabricated by electrospinning and further surface-functionalized with magnetic iron oxide (FexOy) nanoparticles to yield magnetoactive nanocomposite fibrous adsorbents. The latter were characterized in respect to their morphology, mechanical properties and magnetic properties while they were further evaluated as substrates for removing Ofloxacin (OFL) from synthetic aqueous media and secondary urban wastewater (UWW) under varying physicochemical parameters, including the concentration of the pharmaceutical pollutant, the solution pH and the membranes’ magnetic content. The magnetic-functionalized fibrous adsorbents demonstrated significantly enhanced adsorption efficacy in comparison to their non-functionalized fibrous analogues while their magnetic properties enabled their magnetic recovery and regeneration.