AbstractX‐ray diffraction, positron annihilation, electron microscopy and bulk density measurements are reported as a function of the degree of acetylation for a linters cotton. Heterogeneous reaction proceeds with a retention of ordered structure in the fibers. Substitution does increase the extent of disorder but is not sufficiently extensive to disrupt completely order at the fiber, fibril, micro fibril, and crystallite levels. The generation of disorder is associated with an increase in the interfibrillar distance, a breakup of the microfibrillar structure without a total disruption of the microcrystalline structur