AbstractThe amylose content and the chain profile of amylopectin from normal, waxy and high amylose barley starches were determined after enzymatic debranching and gel permeation chromatography and the degree of branching of the amylopectin was analysed by 1H‐n.m.r. spectroscopy. The normal barley starch contained around 30%, the high amylose around 40% and the waxy starch 9% amylose. The amylopectin of the high amylose starches had longer chains than those of the normal or waxy starches, especially in the molecular weight interval 5,400‐8,000, but less of those below 2,400 in molecular weight. The chain length of amylopectin from high amylose barley was on average 5 units longer than those of normal or waxy barleys.