Hemicelluloses such as xylans play an increasing role as renewable raw materials for technological applications. The complex and variable composition of hemicelluloses requires powerful analytical techniques in order to assess their composition. In the present study, the neutral fraction of hydrothermally isolated xylan from beech wood was characterized by capillary electrophoresis with laser-induced fluorescence detection (CE-LIF) upon derivatization with 8-aminopyrene-1,3,6-trisulfonic acid. Reproducible separation of the xylo-oligosaccharides was achieved using a polyvinyl alcohol coated capillary and a 25 mM sodium acetate buffer, pH 4.75, as background electrolyte at an applied voltage of -30 kV. Intermediate precision expressed as relative standard deviation was below 2.0 % for migration times and below 10 % for relative peak areas except for the oligomers present at very low concentrations only. At the same time, derivatization conditions proved to be robust as well. Samples obtained by fractionation of the xylan were subsequently characterized by CE-LIF. In addition, capillary electrophoresis with mass spectrometry detection indicated the presence of small amounts of xylo-oligosaccharides containing additional sugar moieties such as 4-O-methylglucuronic acid. Moreover, minor components containing acetyl groups could be detected. The presence of these impurities was confirmed by nuclear magnetic resonance analysis of the fractions. In conclusion, although none of the techniques applied here gave a complete picture of the composition of the investigated xylan or its fractions, the combination provided insight into the complexity of the sample.