Diode array detection (DAD) in capillary electrophoresis (CE) offers similar advantages over single-wavelength detection as it does in high performance liquid chromatography (HPLC). Thus, confirmation of compound identity and establishment of peak purity are critical issues in CE, necessitating sensitive and specific detection. With an optimized optical system, DAD yields sensitivity comparable to that of single or variable wavelength detectors. Sensitivity can be further improved three to five times by use of expanded pathlength capillaries employing the so-called bubble cell. Optimization of optical design, as well as maintenance of spectral fidelity, will be discussed in this work. A variety of applications of CE, and specifically of micellar electrokinetic capillary chromatography (MEKC), with emphasis on quantitative analysis, sensitivity, linearity, spectral identification, and peak purity verification will be presented. The use of spectral information for peak tracking in MEKC method development and for the assessment of purity of electrodistorted peaks will also be illustrated.