In order to prepare physiologically tolerated water-soluble starch esters, the invention proposes that starch is converted by acid hydrolysis or enzymatic hydrolysis to a partially hydrolysed form with a mean molecular weight in the range from 10,000 to 500,000 Daltons. This partial hydrolysate is then acylated, in aqueous solution, with the anhydride or halide of an aliphatic monocarboxylic acid with 2 to 4 carbon atoms or an aliphatic dicarboxylic acid with 3 to 6 carbon atoms, or mixtures thereof, and an alkalinization agent, to give a product with a substitution ratio in the range from 0.1 to 1.0 mole/mole. Salts are removed from the resulting reaction mixture. The starch esters thus obtained are highly suited for clinical use, in particular parenteral administration and administration in the diet.