Metabolomics, understood as a data driven strategy trying to find markers of a situation under study without a priori hypothesis, has rapidly caught the attention and evolved from the simple pattern recognition strategy, which was a great innovation at its origins, to the interest for the final identification of markers responsible for class separation, i.e., from data to knowledge. Due to differences in physico-chemical properties and concentrations of the metabolites, but also due to differences in matrix properties, cross-platform approaches are proving to increase the capability of information. Once more techniques do not compete. This is the scene where capillary electrophoresis (CE) has its niche to provide information mainly on polar or ionic compounds in biological fluids. General advantages and disadvantages of CE for sample fingerprinting will be discussed and methods will be classified depending on the detection system (UV or MS) as this strongly affects all the conditions. Recent developments will be presented in different biological fluids, although urine is without a doubt the preferred sample for CE analysis.