One of the examples of physical starch modifications is the retention of a starch suspension in water having a temperature slightly lower than the pasting temperature (annealing). The aim of this study was to investigate the effect of the annealing process performed at various temperatures as the first stage of starch modification. The annealed starch preparations were then esterified using acetic acid anhydride. Finally, the annealed and acetylated starch preparations were determined for their properties. The annealing of starch before acetylation triggered changes in the properties of the modified preparations. It contributed to a higher degree of starch substitution with acetic acid residues and to the increased swelling power of starch. Both these properties were also affected by the annealing temperature. The highest resistance to amylolysis was found in the case of the starch preparation annealed at 53.5 °C and acetylated. The double modification involving annealing and acetylation processes increased the onset and end pasting temperatures compared to the acetylation alone. Similar observations were made for the consistency coefficient and yield point.