An analytical method based on the combination of solid-phase extraction (SPE) and field-amplified concentration (FAC), with micellar electrokinetic chromatography (MEKC) was developed to extract, concentrate, separate, and quantitate six organonitrogen pesticides (metribuzin, bromacil, terbacil, hexazinone, triadimefon, and DEET) in drainage water. The recovery of the first five pesticides was over 85%, and the limit of detection was 0.8 ppb. Four advantages (enhanced enrichment and recoveries, reduced extraction time and interferences) of combining SPE with FAC for trace analysis of pesticides at the ppb level were demonstrated.