In aqueous capillary electrophoresis selectivity between different alkyl chain lengths within one anionic surfactant-group markedly exceeds selectivity between different functionalities at a given chain length. Peak identification and quantitative analysis in complex mixtures is almost impossible, especially, if the sample contains ethoxylated surfactants as well. Applying nonaqueous capillary electrophoresis (NACE), significant differences in the mobilities of the various functionalities can be generated to exceed at satisfying separation. In this paper, method development of NACE systems is described and the application of these systems to anionic surfactant analysis in real sample matrices is documented.