In this work, magnetic graphene composites were synthesized by a one-step hydrothermal reaction. The magnetic graphene composites used as the adsorbents for PAEs analysis have several advantages including high adsorption capacity and good extraction ability. After the investigation of the extraction conditions, a rapid and sensitive method for the determination of PAEs was established by MSPE coupling with GC–MS. Finally, the proposed method was successfully applied for the analysis of PAEs from environmental water.