A simple approach is presented based on the in-line coupling between magnetic particles-based SPE and CE. Silica-coated iron oxide particles functionalized with C-18 were successfully synthesized and used as a reverse-phase sorbent for in-line SPE-CE. Magnets were used to locally immobilize these sorbents inside the capillary. Four drugs of abuse were preconcentrated and determined in urine samples using the developed method with a simple pretreatment procedure based on LLE. Several parameters affecting the preconcentration were evaluated. The obtained results show that this strategy enhanced detection sensitivity in the range of 125-700-fold compared with CE without preconcentration. The developed method provides LODs (S/N = 3) for standard samples in the range of 0.520 ng/mL with satisfactory analytical precision, in both intraday and day-to-day experiments (RSDs <20%). The LODs (S/N = 3) reached for urine samples were in the range of 20-50 ng/mL. Relative recoveries greater than 75.9% were obtained. The established method has been applied to the analysis of drugs of abuse in urine samples from drug abusers.