The water-soluble carbohydrate (WSC) that accumulates in the stems of wheat during growth can be an important contributor to grain filling, particularly under conditions when assimilation is limited, such as during end-of-season drought. WSC concentration was measured at anthesis across a diverse set of wheat genotypes over multiple environments. Environmental differences in WSC concentration were large (means for the set ranging between 108 and 203 mg g–1 dry weight), and there were significant and repeatable differences in WSC accumulation among genotypes (means ranging from 112 to 213 mg g–1 dry weight averaged across environments), associated with large broad-sense heritability (H = 0.90 ± 0.12). These results suggest that breeding for high WSC should be possible in wheat. The composition of the WSC, examined in selected genotypes, indicated that the variation in total WSC was attributed mainly to variation in the fructan component, with the other major soluble carbohydrates, sucrose and hexose, varying less. The degree of polymerisation (DP) of fructo-oligosaccharides was up to ~13 in samples where higher levels of WSC were accumulated, owing either to genotype or environment, but the higher DP components (DP > 6) were decreased in samples of lower total WSC. The results are consistent with fructan biosynthesis occurring via a sequential mechanism that is dependent on the availability of sucrose, and differences in WSC contents of genotypes are unlikely to be due to major mechanistic differences.