Thermal modification is a technique to produce wood with increased dimensional stability and lower equilibrium moisture content. 2H NMR relaxation measurements and pulsed field gradient (PFG-NMR) methods are non-invasive spectroscopic techniques that can be used to measure the response of liquid confined in porous materials and yield information on the size and distribution of the pores. These methods were used to study the structure and changes in structure of thermally modified Scots pine wood. The 2H longitudinal relaxation measurements of wood samples at different moisture contents showed different relaxation times and relaxation time distribution in the thermally treated samples. The effect of the thermal treatments on the cell size in wood samples was studied by PFG-NMR measurements with different dwell times. The PFG-NMR measurements showed no clear change in the cell dimensions of the thermally modified samples compared with control samples taken from the same log.