Summary: The novel solvent dimethyl sulfoxide (DMSO)/tetrabutylammonium fluoride trihydrate (TBAF · 3H2O) was studied for acetylation of linters cellulose. In order to control the degree of substitution (DS), acetylation of the macromolecule was carried out at different reaction time and temperature, molar ratio of reactants, as well as under variation of the concentration of TBAF · 3H2O in solution. Cellulose acetate (CA) was accessible with DS ranging from 0.43 to 2.77. The change in concentration of TBAF · 3H2O in DMSO showed a strong influence on DS. The most appropriate reaction conditions for acetylation of linters cellulose regarding maximal DS were evaluated. The structure of the CA was characterized by means of FTIR and NMR spectroscopy. The solubility of the CA depends not only on the DS but also on the reaction conditions applied, indicating a different distribution of acetate moieties both within and between polymer chains.