The complexity of the chemical composition of synthetic macromolecules has increased the need for more reliable analytical methodologies for characterizing these materials. CE has emerged as a powerful analytical tool able to provide useful information about the chemical properties of these complex molecules. Interestingly, such information can be in some cases complementary to that provided by other classical techniques. Thus, in this revision it has been demonstrated that CE is being used in their different modes (FSCE, CGE, MEKC, etc.) to successfully face the tremendous diversity that can be found analyzing synthetic polymers. One of the main characteristics of CE is that this technique makes possible to develop uniquely tailored separation procedures to analyze synthetic macromolecules of very different nature.