Oligosaccharides derived from alkali-extracted sorghum glucuronoarabinoxylan by digestion with a combination of (1-->4)-beta-D-arabinoxylan arabinofuranohydrolase (AXH) and endo-(1-->4)-beta-D-xylanase (Xyl I), both from Aspergillus awamori, were purified by size-exclusion chromatography followed by preparative high-performance anion-exchange chromatography. Structural studies including monosaccharide analysis, methylation analysis, 1H NMR spectroscopy, and mass spectrometry were carried out, resulting in the characterisation of four novel oligosaccharides, namely, alpha-D-GlcpA-(1-->2)-beta-D-Xyl p-(1-->4)-beta-D-Xyl p-(1-->4) -beta-D-Xyl p, alpha-D-GlcpA-(1-->2)-beta-D-Xyl p-(1-->4) [alpha-L-Araf-(1-->3)]-beta-D-Xyl p-(1-->4)-beta-D-Xyl p, alpha-D-GlcpA-(1-->2)-beta-D- Xyl p-(1-->4)-beta-D-Xyl p-(1-->4)[alpha-L-Araf-(1-->2)-alpha)-alpha- L-Araf-(1-->3)]-beta-D-Xyl p-(1-->4)-beta-D-Xyl p, and alpha-D-GlcpA-(1-->2) -beta-D-Xyl p-(1-->4)[alpha-L-Araf-(1-->3] beta-D-Xyl p-(1-->4)[alpha-L-Araf-(1-->2)-alpha-L-Araf-(1-->3)] -beta-D-Xyl p-(1-->4)-beta-D-Xyl p. The various oligosaccharides identified provide additional insight into the structure of sorghum glucuronoarabinoxylan. Furthermore, novel data were generated with respect to the substrate specificity of AXH and Xyl I towards glucuronoarabinoxylans in general.