The aim of the present study was to investigate the mechanism of formation of maize starch (MS)-lipid complexes during pasting in the Rapid Visco Analyser. MS-lauric acid (LA) and MS-monomyristyl glycerol (MMG) samples with lipid concentrations of 0–5% were prepared and characterized. Complexing index (CI) and rheological analyses showed that the viscosity and gel strength of starch was highly correlated to the amount of starch-lipid complex that formed. An increase followed by a decrease in CI values, enthalpy change and structural order during pasting of MS-2% LA mixture indicated that starch-lipid complexes were mostly formed during the setback stage, and that the disruption of some complexes formed at higher lipid concentration occurred with ongoing cooling. This study revealed the mechanisms of formation of starch-lipid complexes during simulated food processing, and how such complexes affect the viscoelastic properties of starch pastes, which is of relevance to the texture of starchy foods.