The water-insoluble fraction of Zea mays L. hybrid B73×Mo17 shoot cell walls, pretreated with purified Bacillus subtilis (1→3), (1→4)-β-D-glucan 4-glucanohydrolase and purified B. subtilis endo-(1→4)-β-D-xylanase, was subsequently treated with a glucuronoxylan xylanohydrolase preparation, all of which were obtained from a commercially available B. subtilis α-amylase (Novo Ban 120). Carbohydrates (about 16% of the original water-insoluble fraction of Zea shoot cell-walls) derived from the enzyme treatment contained significant amounts of galactan and (1→4)-β-D-galactobiose in addition to glucuronoarabinoxylan and neutral sugar residues-containing rhamnogalacturonan fragments. Methylation analysis and partial acid-hydrolysis of the isolated galactan followed by analysis of the hydrolyzate showed that the galactan consisted of about 14 (1→4)-β-consecutively linked galactose moieties.