A bonded phase capillary column containing macrocyclic polyamine, [28]ane-N6O2 functional groups was used for the electrophoretic separation of arsenic, chromium and selenium species. A simple device interfacing this capillary electrochromatography (CEC) systems to an inductively coupled plasma mass spectrometer (ICPMS) is described. The dimension of the capillary column was 160cm×100μm i.d. To accommodate this electrophoretic separation, an auxiliary capillary was used with nitric acid (0.05M) as makeup liquid. With the electrokinetic method at –20kV, 20s and a nebulizer gas flow rate of 1lmin−1, the sample injected was analyzed with an applied potential of −20kV. The background electrolyte buffer for the separation of CrO42−–Cr3+ was phosphate (20mM, pH 6.5). That for HAsO42−–Ph4As+ was pyromellitate (20mM, pH 6.0) and for SeO42−–SeO32− was acetate (20mM, pH 6.0). The role of the buffer’s anion was also discussed. The separation efficiency of the bonded phase was compared with the bare fused silica. Concentration detection limits for these metal ions were in the low ppb range. In addition, the matrix effect of the established system with the bonded phase was found smaller than that with the bare fused silica.