Water interactions and accessibility of the nanoscale components of plant cell walls influence their properties and processability in relation to many applications. We investigated the water-accessibility of nanoscale pores within the fibrillar structures of unmodified Norway spruce cell walls by small-angle neutron scattering (SANS) and Fourier-transform infra-red (FTIR) spectroscopy. The different sensitivity of SANS to hydrogenated ( H 2 O ) and deuterated water ( D 2 O ) was utilized to follow the exchange kinetics of water among cellulose microfibrils. FTIR spectroscopy was used to study the time-dependent re-exchange of OD groups to OH in wood samples transferred from liquid D 2 O to H 2 O . In addition, the effects of drying on the nanoscale structure and its water-accessibility were addressed by comparing SANS results and the kinetics of water exchange between never-dried and dried/rewetted wood samples. The results of the kinetic analyses allowed to identify two processes with different timescales. The diffusion-driven exchange of water in the spaces between microfibrils, which was observed with both SANS and FTIR, takes place within minutes and rather homogeneously. The second, slower process appeared only in the OD/OH re-exchange followed by FTIR, and it still continued after several weeks of immersion in H 2 O . SANS could not detect any significant difference between the never-dried and dried/rewetted samples, whereas FTIR revealed a small portion of OD groups that resisted the re-exchange and this portion became larger with drying. Graphic abstract