The objective of the current work was to evaluate the impacts of dielectric barrier discharge plasma and repeated dry-heat treatments on the acetylation process of corn starch. The combined modification resulted in a higher substitution degree of acetate groups on starch chains compared to the acetylation treatment alone. This outcome was linked to the increase in surface area and structural organization level of granules achieved through the application of plasma and heating/cooling cycles, respectively. The successful esterification of starch structure was verified through FTIR (1710 cm−1) and 1H NMR (2 ppm). With the increase in plasma treatment duration up to 20 min, gelatinization enthalpy increased (10.81 J/g) due to the cross-linking reaction. Starch acetate produced through the combined treatment could find the application in the development of low-calorie food formulations due to its high resistant starch (70.5 g/100 g) and low viscosity (43 mPa s).