A new kind of phenyl-functionalized magnetic fibrous mesoporous silica (Fe3O4@SiO2@KCC-1-phenyl) was prepared by copolymerization as an efficient adsorbent for the magnetic extraction of phthalate esters from environmental water samples. The obtained Fe3O4@SiO2@KCC-1-phenyl showed monodisperse fibrous spherical morphology, fairly strong magnetic response (29 emu g–1), and an abundant π-electron system, which allowed rapid isolation of the Fe3O4@SiO2@KCC-1-phenyl from solutions upon applying an appropriate magnetic field. Several variables that affect the extraction efficiency of the analytes, including the type of the elution solvent, amount of adsorbent, extraction time and reusability, were investigated and optimized. Under optimum conditions, the Fe3O4@SiO2@KCC-1-phenyl was used for the extraction of four phthalate esters from environmental water samples followed by high-performance liquid chromatographic analysis. Validation experiments indicated that the developed method presented good linearity (0.1–20 ng mL-1), low limit of detection (7.5-29 μg L–1, S/N=3). The proposed method was applied to the determination of phthalate esters in different real water samples, with relative recoveries of 93-103.4% and RSDs of 0.8–8.3 %.