Recent developments in capillary electrophoresis coupled to mass spectrometry (CE2MS) are reviewed from over 400 references covering the significant challenges, issues, and results obtained with CE2MS analyses. A particular attention is paid to instrumental aspects for successful hyphenation of CE with MS,regarding interfaces and ionization sources. A special section is dedicated to quantitative results, and various methodologies to achieve sensitive and repeatable analysis are considered. Dedicated applications of capillary zone electrophoresis (CZE) coupled to MS are discussed, particularly in the field of drug analysis. Development of other capillary-based electrodriven separation techniques such as non-aqueous capillary electrophoresis (NACE), micellar electrokinetic chromatography (MEKC), and capillary electrochromatography (CEC) hyphenated with MS are also treated. The successful coupling of these electromigration schemes with MS detection provides an efficient and sensitive analytical tool for the separation, quantitation, and identification of numerous pharmaceutical, biological, therapeutic, and environmental compounds. Chip-based microdevices are finally discussed, regarding fabrication methods, designs, MS interfacing, and applications. Current capabilities and limitations for future use are emphasized considering improvements in methodology and instrumentation.