This paper presents a successful demonstration of the on-line coupling of MEKC (micellar electrokinetic chromatography) to ESIMS (electrospray ionization mass spectrometry) for the quantitative analysis of seven s-triazine herbicides. The on-line MEKC-ESIMS was used to determine the structure of CE-separated peaks of seven triazine herbicides. The mixture of triazine herbicides was separated in a 20 mM sodium borate buffer (pH 8.5) containing 15 mM sodium dodecylsulfate (SDS) by using a bare fused-silica capillary. Electrospray ionization mass spectrometer was operated in the positive-ion mode when the mass spectra of seven triazine herbicides were observed from each peak, and the solution of water-methanol-formic acid (50/49/1 v/v/v) was used as a sheath liquid. The effects of SDS concentration, the run buffer pH, and the electric field on the separation of seven s-triazine herbicides were investigated. The MEKC-ESIMS detection showed 5 to 10 times higher sensitivity compared to the MEKC-UV detection. In addition, it did not need any pretreatment step.