The development and applicability of the hyphenated technique combining the high separation capability of capillary electrophoresis (CE) to the greatly sensitive elemental detection of inductively coupled plasma mass spectrometry (ICP-MS) is presented. The successful implementation of CE-ICP-MS was embossed by projecting an efficient interface to transfer the low volumes of separated species from the CE capillary to the plasma, maintaining their resolution. Improvements on the CE-ICP interfaces along the last fifteen years are presented. Further, instrumental improvements for data acquisition of fast transient signals and those for lessening interferences in CE-ICP-MS applications for separation and identification of arsenic, chromium and selenium species are described. Papers describing the ability of CE to separate small biomolecules and the identification of chemical species by a tag element such as sulfur and phosphorus determined by ICP-MS are presented. Applications to identify metallothioneins isoforms are pearly described, as well as quantification of metalloproteins and metallodrugs in biological samples. Recent applications of CE-ICP-MS to calculate stability constants of radiochemical compounds and their complexation with humic and fulvic acids to evaluate nuclear waste disposal were included.