Drying of chemical pulps results in a decreased swelling of the fibres, leading to lower density and strength properties of paper sheets. To investigate how variation of pulp pH, drying process temperature, and final moisture content affect this phenomenon, structural studies were performed on a cellulose-rich pulp. Interrupting the drying at moisture contents of around 20%, using drying temperatures of 80 °C and 140 °C, resulted in a more severe degree of hornification than if the pulp was completely dried at the same temperatures. This increased loss of swelling was accompanied by increased cellulose microfibril aggregation. No change of the cellulose microfibril size or of the cellulose crystallinity, as determined by NMR, could be seen. Further, the accessibility of the cellulose microfibril surfaces, including surfaces between microfibrils, was unaffected by the drying. Thus, hornification should not primarily be related to a reduction of accessible cellulosic surfaces.