The structural and mechanical properties of compression-molded normal and high-amylose maize starches were studied as a function of processing water content and ageing time. Rubbery thermoplastic starches were produced by compression molding of four maize starches with differences in amylose content and amylopectin structure. Glycerol (30% on the basis of dry starch) and water (between 10 and 35% on the basis of total mass) were used as plasticizers. After processing, the amorphous thermoplastic starch materials crystallized during ageing. The semicrystalline materials contained both E-type and V-type, as well as B-type crystallinity. The properties of the thermoplastic starch materials are dependent on water content during processing, starch source, and ageing time. The normal maize starch materials are highly flexible with elongations between 56 and 104%. The elongations of the high-amylose maize starch materials were between 5-35%. The tensile stress and E-modulus of the normal maize starch materials were in the range of 3.9-6.7 and 27-131 MPa, respectively. The tensile stress and E-modulus of the high-amylose maize starch materials increased from approximately 0.5 to 23 and 5 to 700 MPa, respectively, with increasing water content during processing from 10 to 35%. The differences in mechanical properties of the normal and high-amylose materials were explained by differences in the structure of the amylose and amylopectin structure. It was concluded that both lead to differences in the starch network.