Monolithic columns were successfully prepared and used with capillary electrochromatography for the analysis of 3,4-methylenedioxymethamphetamine (MDMA) in ecstasy tablets and its metabolites in urine samples. Cationic and neutral monolith columns provided better efficiencies than anionic monoliths. The neutral butyl methacrylate (BMA) monolith column provided symmetrical peaks with the highest efficiency, high resolution and short analysis times. The developed method using BMA monolithic column provided the detection limits for MDMA and its metabolites at 1 µg mL^-1 with excellent intra-day and inter-day precision and linearity from 7.5 to 100 µg mL^-1 (R² ≥ 0.99). MDMA was found as the main component in ecstasy tablets while 4-hydroxy-3-methoxymethamphetamine as the major metabolite in urine samples. High recoveries (97% for MDMA from tablets and 84 - 102% for its metabolites from urine samples) were obtained using simple ultrasonic extraction for ecstasy tablets and liquid.liquid extraction for urine samples.