The enzyme-resistant starch (ERS) content in processed high amylose and regular maize starches has been studied, with and without acid dextrinisation. The physicochemical and structural characteristics of the starches were analysed using a variety of techniques. The increase in ERS in high amylose maize starch with dextrinisation was related to the formation of a critical molecular weight fraction (MW ~ 20,000) that could rearrange structurally. Further dextrinisation reduced the processed starch MW to below where it could still form ERS. Regular maize starch containing less than 30% amylose did not increase its resistance to amylase digestibility with acid dextrinisation, probably due to impairment of amylose rearrangement by the numerous branched amylopectin chains. The ERS, which is likely to form during the enzyme-digestion process, is a linear molecule with a maximum degree of polymerisation (DP) of 30, irrespective of the starch source, processing conditions applied or type and amount of acid used. © 2010, Elsevier Ltd.