A novel magnetic material Fe(3)O(4)/SiO(2)/P(MAA-co-VBC-co-DVB) was prepared via the hypercrosslinking of its precursor which was produced via precipitation polymerization of methacrylic acid (MAA), vinylbenzyl chloride (VBC), and divinylbenzene (DVB) in the presence of Fe(3)O(4)/SiO(2) submicrospheres with the surface containing abundant reactive double bonds. The resultant sorbent was characterized by scan electron microscopy, N(2) adsorption, and Fourier transform infrared spectroscopy. It was found that this material had remarkable features such as large surface area (500 m(2)/g) and pore volume (0.32 cm(3)/g), as well as desirable chemical composition (including hydrophobic and ion-exchange moieties). Taking advantages of the Fe(3)O(4)/SiO(2)/P(MAA-co-VBC-co-DVB), a magnetic SPE (MSPE) coupled with capillary electrophoresis (CE) method was developed for the determination of illegal drugs in urine samples. The extraction time could be clearly shortened up to 3 min. The recoveries of these drug compounds were in the range of 84.0-123% with relative standard deviations ranging between 1.7 and 10.5%; the limit of detection was in the range of 4.0-6.0 μg/L. The proposed method is simple, effective, and low-cost, and provides an accurate and sensitive detection platform for abused drug analysis.