AbstractSamples of sorghum (Sorghum bicolorMoench ×Sorghum sudanenseStapf, cv ‘P 988’) were harvested at five growth stages. Quantitative methylation and acetalation–methylation methods were used to examine changes during growth of cell‐wall polysaccharides, their association with phenolic compounds and the effects of changes on rumen degradability. Cellulose degradability, as measured by a nylon‐bag method, decreased from 82·5% at the youngest stage to 36·5% at the milk‐ripe stage, at a greater rate of change than degradability of dry matter. Among the monosaccharides contributing to cell‐wall polysaccharides, the degradabilities of arabinose and uronic acid residues were consistently higher than those of xylose and glucose, the main components of structural carbohydrates. Recovery of parent neutral sugars from cell wall polysaccharides, calculated as the sum of partially methylated alditols, was in good agreement with the values obtained by direct estimation of individual sugars as their alditol acetate derivatives. Total non‐starch polysaccharide content increased from 31·1% to 45·1% between the first two growth states, with little change evident thereafter. The relative proportion of individual to total sugars remained consistent throughout growth. The values for arabinose, xylose and glucose residues accounted for 4·9%, 27·9% and 63·0% of total neutral sugars, respectively. The pattern of glycosidic linkages detected could be mainly ascribed to the presence of (1–4)‐β‐D‐glucans (cellulose), arabinoxylan, (1–3)(1–4)‐β‐D‐glucans, (1–4)‐β‐D‐galactan, (1–3)(1–6)‐β‐D‐galactan, rhamnogalacturonan and, possibly, xyloglucan. The cellulose content of the five sorghums was, in order of growth, 14·3%, 21·8%. 22·3%, 21·2% and 22·0% of dry matter.The ratio of the mixed‐linked g1ucan:cellulose decreased during growth. Arabinoxylan, the predominant hemicellulosic polysaccharide, was estimated to comprise about 33% of total neutral sugars consistently for all sorghum samples. Arabinose, found largely as terminal residues in the cell walls, carried various amounts of alkali‐labile substituents, particularly at position 0–5, depending on the growth stage of sorghum. The extent of 0–5 substitution was closely correlated with both the lignin content (total phenolic