Various non UV-Active hydroxylated and amino-containing (monomers and polymers) compounds were derivatized with phthalic anhydride (pre- or in-column) to allow CZE–diode array detection analysis. The derivatization procedure, using imidazole and pyridine to catalyze phthalation, leads to fast and complete derivatization. The alcohols are UV-inactive and are not charged. The amines can be charged, but they also lack UV-sensitivity. The result of phthalation is the insertion of a chromophore (phenyl group) and an ionic functionality (carboxyl) into the compounds under investigation. In this manner, using pre-column derivatization, it is possible to separate mixtures of monomeric alcohols and amines. Due to the high efficiency, inherent to CE, it is also possible, on the basis of the difference in electrophoretic mobilities, to investigate the distribution in the chain length of synthetic poly(ethylene glycol) and poly(oxyalkylene)amine polymers. A successful attempt was made to use in-column derivatization for the analysis of the amino-containing monomers and polymers. Analyses were performed on bare fused silica, as well as on wall coated capillaries.