Cellulose acetates have been investigated on different structural levels. Based on the determination of the acetate pattern of the monomers, a method has been developed to describe the distribution of the acetyl groups in the polymer chain. This approach comprises permethylation with methyl triflate, deacetylative deuteromethylation under alkaline conditions, random cleavage, remethylation with methyl-d(3), FAB-MS analysis and comparison of the experimental data with those calculated for a random acetate pattern. Results are discussed with respect to the conditions of the acetylation reactions.