Carbon-13 high-resolution solid-state NMR techniques have been invaluable in elucidating the structure of regenerated cellulosic materials. Studies of a range of fibres have shown systematic changes in chemical shifts, which can be related to the influences of physical processing or chemical modification. A constrained curve fitting method has been applied, where the C4 spectral envelope is represented as the sum of contributions from polymer in ordered, partially-ordered and disordered environments, associated with differing conformational arrangements of the cellulose hydroxymethyl and glycocidic bonds. The empirical gamma-gauche effect seems likely to provide the best rationalization for the relationship between C4 shifts and conformational order, taking into account the increased range of bond angles in disordered environments. The quantification of proportions of polymer units within different conformational groupings will provide new insights into the development of supramolecular texture. This will allow better appreciation of the relationships between fibre processing and ultimate fibre performance. (c) 2007 Elsevier Ltd. All rights reserved.