The development and analytical characterization of a coupled capillary electrophoresis-inductively coupled plasma sector field mass spectrometer (CE-ICP-SFMS) system for the simultaneous determination of different species of As, Sb, Se and Te at trace levels are described. The species are separated by CE using a 55 cm×75 µm id fused silica capillary column. A newly developed interface with a special, low dead volume spray chamber allows the optimization of the fluid mechanical properties, thus preventing a suction effect between the nebulizer and the CE capillary. The ICP-SFMS instrument runs in the low resolution mode and is equipped with a grounded platinum electrode at the ICP torch in order to achieve the highest possible sensitivity. The CE-ICP-SFMS system developed provides stable electrophoretic conditions and allows reproducible separations to be obtained with RSDs below 3% for the migration times and below 8% for the peak areas. Excellent peak shapes down to 4 s and short analysis times of a few minutes are other important features of this combined instrument. Detection limits in the low µg L ^–1 region for compounds and in the picogram to femtogram range for the isotopes are achieved from standard solutions.