We have prepared a solid phase for the extraction of chlorobenzenes (CBs) by coating magnetic (Fe3O4) nanoparticles with silica via a sol-gel process using a mixture of tetraethoxysilane and triethoxyphenylsilane. The nanoparticles were characterized by SEM, energy-dispersive spectroscopy, and X-ray diffractometry. The nanoparticles were used for the extraction of 1,4-dichlorobenzene (1,4-DCB), 1,2,3-trichlorobenzene (1,2,3-TCB), 1,2,4-trichlorobenzene (1,2,4-TCB), and 1,2,3,4-tetrachlorobenzene (1,2,3,4-TeCB) from water, followed by their determination by GC-electron capture detection. Under optimal conditions, enrichment factors ranging from 220 to 360 were obtained. All determination coefficients (r2) are >0.99, and linear response is found in range 0.025–1.5 μg/L (at the lower end), and 6–120 μg/L (at the higher end). Detection limits are 6, 10, 11, and 500 ng/L for 1,2,3,4-TeCB, 1,2,4-TCB, 1,2,3-TCB, and 1,4-DCB, respectively. All RSDs are <6% (for n = 5). The method was successfully applied to the determination of CBs in environmental water samples.