The main objective of this study was to evaluate the effect of sample preparation on cell-wall density and porosity using gas pycnometry. Native and thermally modified twin samples of Norway spruce (Picea abies (L.) Karst.), sycamore maple (Acer pseudoplatanus L.), and European ash (Fraxinus excelsior L.) were analyzed. The samples differed in terms of shape, geometry, and climatic state. On the one hand, the samples were oven dry as usual and, on the other hand, conditioned at 22 °C and 95 % relative humidity. Furthermore, the samples were processed using solvent exchange drying. In addition to helium, nitrogen was used as a displacement gas. The tests show i.a. how this can lead to misinterpretation of the cell-wall density or porosity of wood determined by gas pycnometry. The results show that native spruce has a lower cell-wall density and higher porosity compared with native maple and ash. Due to thermal modification, the cell-wall densities are decreased. The investigations show that the determined cell-wall density and porosity of the wood are strongly dependent on the sample geometry and climatic state. The cell-wall densities of all investigated wood species in the conditioned state at 22 °C and 95 % relative humidity are significantly higher compared with the oven-dry cell-wall densities.