The effect of extractives removal on liquid sorption, swelling and surface energy properties of unmodified wood (UW) and thermally modified Scots pine heartwood (hW) (TMW) was studied. The extraction was performed by a Soxtec procedure with a series of solvents and the results were observed by the multicycle Wilhelmy plate method, inverse gas chromatography (IGC) and Fourier transform infrared (FTIR) spectroscopy. A significantly lower rate of water uptake was found for the extracted UW, compared with the unextracted one. This is due to a contamination effect in the latter case from water-soluble extractives increasing the capillary flow into the wood voids, proven by the decreased water surface tension. The swelling in water increased after extraction 1.7 and 3 times in the cases of UW and TMW, respectively. The dispersive part of the surface energy was lower for the extracted TMW compared to the other sample groups, indicating an almost complete removal of the extractives. The FTIR spectra of the extracts showed the presence of phenolic compounds but also resin acids and aliphatic compounds.