We describe here the state-of-the-art development of on-line capillary electrophoresis-mass spectrometry (CE-MS) over the last two years. Technological developments included are novel designs of new interfaces and ionization sources, new capillary coatings, buffers, and micelles as well as application of various modes of CE-MS published in the recent literature. The areas of CE-MS application in analysis of small achiral and chiral solutes are covered in sections that highlight the recent advances and possibilities of each mode of CE-MS. Application areas reviewed in this paper include achiral and chiral pharmaceuticals, agrochemicals, carbohydrates, and small peptides. The separation of enantiomers using micellar electrokinetic chromatography (MEKC)-MS with molecular micelles and capillary electrochromatography (CEC)-MS using pack tapered columns appears to provide good tolerance to electrospray stability for routine on-line CE-MS. These two modes seem to be very suitable for sensitive detection of chiral pharmaceuticals in biological samples, but their use will probably increase in the near future. Overall, it seems that one mode of CE-MS, in particular capillary zone electrophoresis (CZE)-MS, is now recognized as established technique for analysis of small charged solutes, but other modes, such as MEKC-MS and CECMS, are still within a period of development in terms of both MS-compatible pseudostationary phases and columns as well as applications.