► Using Fe3O4@GO as the sorbent of MSPE. ► The first time using Fe3O4@GO to adsorb trace levels of PCBs in water samples. ► Investigation of Fe3O4@GO’s adsorption characteristics and sorption isotherm. ► Establishment of a highly selective and sensitive MSPE–GC–MS analytical method. In this paper, Fe3O4 nanoparticle (Fe3O4 NPs) grafted graphene oxide (Fe3O4@GO), are successfully synthesized and used for the extraction of 2,4,4′-trichlorobiphenyl (PCB 28) from a large volume of water solution. With the magnetic solid-phase extraction (MSPE) technique based on the Fe3O4@GO sorbents, it requires only 30min to extract trace levels of PCB 28 from 200mL water samples. The Fe3O4@GO was analyzed by using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier Transform infrared (FT-IR) spectroscopy, and Vibrating sample magnetometer (VSM), specific surface area analyzer. The adsorption kinetics, adsorption capacity of the adsorbent, and the effect of the solution pH and desorption conditions on the removal efficiency of PCB 28 were investigated. The second-order kinetic equation best describes the sorption kinetics. The results showed that Fe3O4@GO was a suitable material in the pre-concentration and immobilization of PCB 28 from large volumes of aqueous solutions in polychlorinated biphenyl pollution cleaning.