In this work, porous polyethersulfone (PES)/polyethylene glycol (PEG) ultrafine fibers were prepared via electrospinning technique, and then were used to removing endocrine disrupters from their aqueous solutions. The surface and the internal structures of PES/PEG ultrafine fibers were characterized by scanning electron microscopy (SEM) and the result showed that they were both porous. The porous electrospun PES/PEG ultrafine fibers can remove endocrine disrupters such as biphenyl A (BPA) and biphenyl (BP) effectively. Compared with pure PES ultrafine fibers, PES/PEG ultrafine fibers showed larger adsorption capacity and faster kinetics of uptaking target species. The hydrophilic properties and the porosity of porous PES/PEG ultrafine fibers can be controlled by adding hydrophilic materials such as polyethylene glycol (PEG), which can improve the adsorption properties of porous PES/PEG ultrafine fibers significantly. The results showed that porous electrospun PES/PEG ultrafine fibers had the potential to be used in environmental application and water treatment.