Commercially available cellulose (Avicell PH101) was successfully acylated under homogeneous solution conditions by the following procedure: 2.0 g of cellulose were stirred with 75 mL of N,N-dimethylacetamide for 1 h at 150 degrees C, 3.5 g of LiCl were added, the temperature was raised to 170 degrees C, ca. 18.5 mL of the solvent were distilled and the suspension was cooled to room temperature and stirred overnight. The temperature of the clear cellulose solution was raised to 110 degrees C, kept at that temperature for 1 h, an acid anhydride was added and the solution stirred at 110 degrees C for additional 4 h. Acetates, propionates, butyrates, and acetate/propionate mixed ester were prepared with excellent control of the degree of substitution, DS, 1 to 3 for acetates, 2 and 3 for propionates and butyrates, and 3 for acetate/propionate. The degree of polymerization of cellulose is negligibly affected under these reaction conditions. The distribution of the acetyl moiety among the three OH groups of the anhydroglucose unit shows a preference for the C-6 position.