Samples of 12 varieties of barley from 12 experimental stations in Canada were analysed for starch, barley extract, and crude cellulose plus lignin. Nine six-rowed varieties averaged 3.4% lower in starch, 3.7% lower in extract, and 1.4% higher in cellulose plus lignin than three two-rowed varieties. Maximum and minimum values of the means for the six-rowed varieties were: starch, 55.0% and 52.4%; extract, 77.2% and 74.3%; and crude cellulose plus lignin, 11.3% and 10.1%. Environment had a significant effect. Maximum and minimum values for station means were: starch, 59.2% and 51.7%; extract, 80.8% and 73.6%; crude cellulose plus lignin, 11.0% and 9.6%.Correlation coefficients of carbohydrate fractions with total nitrogen were not significant between varieties but highly significant within varieties for starch r = − 0.95, and extract, r = − 0.91. Partial coefficients, independent of nitrogen between starch and 1000-kernel weight, were significant: between varieties, 0.62; within varieties, 0.75. Those with crude cellulose plus lignin did not attain significance.Starch and barley extract are closely associated within varieties, r = 0.961, and between varieties, r = 0.982. The insoluble cellulose-lignin fraction gave negative inter-varietal associations with starch, r = − 0.952, and barley extract r = − 0.968. Similar relations within varieties are obscured in the simple coefficients but the corresponding partials independent of total nitrogen are significant.