Capillary electrophoresis (CE) is presented as an efficient and potent alternative to other chromatographic techniques, such as liquid chromatography (LC) or gas chromatography (GC), to analyze organic pollutants in environmental samples. Despite the insufficient sensitivity associated with the use of CE with optical detection, the latest developments on the use of alternative detection systems and/or sample preconcentration techniques together with its efficiency and versatility have demonstrated the potential of CE to face the determination of pollutants at trace levels. Other interesting characteristics of CE in the field of environmental analysis include its enormous possibilities to achieve stereoselective analysis of chiral compounds and the low amount of reagents needed (green analytical technique). Nowadays, a large number of research works have been published dealing with the use of CE as a powerful technique for pollutants analysis. This article presents the fundamentals of CE techniques as well as the main developments and applications performed in environmental analysis during the past 10 years. The CE determination of a large variety of organic pollutants, including pesticides, phenols, pharmaceuticals, nitroaromatic compounds, amines, and so on, is described.