Thealpha-amylolysis of gelatinized waxy barley starch and the gelation of the hydrolysates was studied. The progress of the hydrolysis was monitored with gel permeation and ion exchange chromatography. Initial attack occurred mainly between the clusters, without significant hydrolysis of the external chains. The stiffness of 20% gels prepared from the polymeric products decreased with increasing hydrolysis of the amylopectin. A linear relationship between the shear modulus and the original high-molecular weight amylopectin content was observed. Although the branched degradation products of amylopectin (average DP <6×104) were not involved in network formation, they retained their ability to recrystallize as analysed by differential scanning colorimetry. For more extensively hydrolysed products (average DP <5000) no recrystallization or gel formation was observed under the conditions tested. Information on the gel structure was obtained with acid hydrolysis and ion exchange chromatography. The structure of the acid-resistant gel residues was complicated, showing a five-peak distribution when analysed with ion exchange chromatography. No differences between the original and hydrolysate gels was observed. The gel residues were resistant to isoamylase.