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This paper deals with the determination of the capillary pore-size distribution (CPSD) and equilibrium moisture content (EMC) of untreated and thermally modified (TM) Norway spruce [Picea abies (L.) Karst.] by means of the pressure plate technique (PPT). Desorption experiments were conducted at very high values of relative humidity (RH) in the range between 99.2% and 100%. The thermal modification of spruce results in an alteration of the CPSD, owing to the formation of intercellular cracks in the middle lamella, as a result of cell-wall compression. The desorption curves for both untreated and TM spruce show an extremely upward bend at 99.97% RH. This step reflects an EMC of 38.1% for untreated spruce and 33.8% for TM spruce. None of the samples shrunk during the PPT measurements. Following desorption experiments at 97.4% RH, all samples shrunk. This step reflects an EMC of 27.9% for untreated spruce and 21.7% for TM spruce.