Cell wall material was isolated from the pericarp of unripe and ripe tomatoes, free from intracellular compounds and active wall degrading enzymes. The wall preparations were sequentially extracted with cyclohexane-trans-1,2-diaminetetra-acetate (CDTA) at 20°, 0.05 M Na2CO3 at 1°, 0.05 M Na2CO3 at 20°, and 0.5, 1 and 4 M KOH at 20° to leave the α-cellulose residue, which contained a significant amount of pectic material. The polysaccharides isolated from the extracts were fractionated by anion-exchange chromatography and selected fractions were subjected to methylation analysis. The CDTA-soluble pectic polysaccharides had slightly-branched rhamnogalacturonan back-bones compared with the sodium carbonate-soluble pectic polysaccharides. The side chains of the pectic polysaccharides were mainly composed of β-(1→4)-Iinked galactopyranosyl and α-(1→5)-Iinked arabinofuranosyl residues, and the evidence for this was obtained by both methylation analysis and 13C NMR spectroscopy. The major hemicellulosic polysaccharide was a xyloglucomannan and there was evidence for the occurrence of a small amount of a xylan-pectic complex. The ripe fruit contained much less pectic galactans compared with the unripe fruit, and there was a significant decrease in the content of galactan side-chains of the ripe fruit. The hemicelluloses of the unripe and ripe fruit, however, showed negligible difference in composition. © 1990.