In this work, magnetic Fe3O4@mesoporous SiO2 (Fe3O4@mSiO2) microshperes with phenyl group-functionalized interior pore-walls were synthesized through a facile one-pot co-condensation approach, and were successfully used as solid-phase extraction (SPE) sorbents to the extraction and enrichment of bisphenol A from human urine.The obtained phenyl group-functionalized Fe3O4@mSiO2 microspheres possess abundant silanol groups in the exterior surface and numerous phenyl groups anchored in the interior pore-wails, as well as a large surface area (273.5 m2/g), superparamagnetism and uniform mesopores (3.3 nm), which make them promising SPE absorbents for efficient extraction and preconcentration of aromatic compounds from complex biological samples such as human unne.