Naturally sourced products introduced to human nutrition and rediscovered for therapy include polysaccharides from potatoes. The starch may obtain unique properties via acetylation with acetic anhydride at 13 cm 3/100 g of starch as the basic dose of reagent used in industrial conditions. The hydrogel formulation was applied as a carrier for escin included in the dry extract of Aesculus hippocastanum. Six hydrogels were evaluated (methylcellulose, polyacrylic acid-Carbopol 980 NF and polyacrylate crosspolymer 11—Aristoflex Velvet) with various concentrations of the modified starch. The kinetic studies of in vitro β-escin release were carried out in purified water at 37 ± 0.5 °C using a paddle apparatus at 50 rpm and a time period of 7 h. The criterion for the most suitable model was based on a high correlation coefficient of evaluated release profiles. The addition of modified annealed acetylated potato starch resulted in prolongation of β-escin release.