Despite of obvious advantages, capillary electrophoresis (CE) is often considered as an alternative analytical technique only then if more established approaches such as HPLC fail to show satisfactory results. Yet, CE offers enormous variability with respect to separation and detection mode, combined with high efficiency, speed, and ease of operation. Depending on the type of analytes investigated, the analyst can choose from an array of different buffer systems (e.g., aqueous, nonaqueous, ionic liquids, or microemulsion), additives (e.g., organic solvents, tensides, or cyclodextrins), detectors (e.g., UV–vis, fluorescence, or mass spectrometry), and formats (e.g., fused silica capillary, microchip, or monoliths), so that nearly any separation problem will be resolvable. Major disadvantages CE is often associated with are diminished reproducibility and sensitivity. That they can be well handled once all methodological aspects are optimized is summarized in this chapter. A brief introduction to the technique, highlighting technical and practical aspects, is followed by the presentation of successful applications on the separation of natural products in medicinal plants or respective products. They are convincing evidences for placing CE in the group of established and useful analytical techniques rather than only in the niche for exotics.