Thermal analysis of rice starch/1-monoglyceride mixtures at intermediate water content (50%) was carried out using Differential Scanning Calorimetry (DSC) and Thermo-Mechanical Analysis (TMA). The DSC thermal profiles revealed multiple melting characteristics for the amylose-monoglyceride complexes. A mechanism based on partial melting followed by recrystallization (exothermic effect) and remelting is invoked to explain such behavior. Crystallization of amylose-lipid complexes occurs during starch gelatinization with a rate that is determined by the molecular nucleation step. The latter is strongly dependent on the nature of the complexing ligand molecule. Monoglycerides of good amylose complexing ability rapidly induce metastable (small size and/or less perfected) crystallites in the melted polysaccharide matrix which are inclined to reorganization/annealing on subsequent heating in the DSC. The overall thermal behavior of these systems is best rationalized by considering the interactions between solvent and polymer, the morphology of the semicrystalline structure, as well as the kinetic effects inherent with the dynamic character of the thermoanalytical techniques employed. Due to the irreversible/non-equilibrium melting of amylose-lipid complexes, complications can arise in attempting to analyze melting data by the polymer-diluent method (Flory-Huggins equation). The general features of the TMA volume expansion curves suggested that lipids can retard granule swelling at low temperatures.