A methodology using capillary electrophoresis with tandem mass spectrometry detection (CE-MS/MS) was developed, and applied to determine the cocaine content of seized drugs. The cocaine separation among other concomitants by capillary electrophoresis was achieved in just 4.0 minutes using 30 mM ammonium formate, pH 6.5, as a background electrolyte (BGE). The correlation coefficient of the calibration curve in the range of 0.02 to 1 μg/mL was upper 0.999, and the limits of detection (LOD) and limits of quantification (LOQ) were 0.003 μg/mL and 0.01 μg/mL, respectively. The relative standard deviation repeatability (intraday and interday) was less than 6.5% (peak area). The analysis of seized suspected illegal drugs revealed the presence of cocaine in 93% of samples (n = 11), in amounts ranging from 0.04 to 429 mg/g, showing a high variability of concentrations of cocaine. The user can change the provider and, due to the large variability of concentration, be lead to an accidental overdose