Wood is the most important, industrially used renewable resource on the planet, but the aging mechanism of biopolymers on cell walls is poorly understood. Adhesion properties are of critical importance for wood and many other lignocellulosic materials. We used atomic force microscopy and defined the jump-off force ratio in the retract force-displacement curve to study the adhesion force phenomenon and the effects of heat treatments. Here, we identified two sigmoidal curves describing the shift of the adhesion force and the jump-off force ratio: the first curve was attributed to the movement of extractives and the second to the degradation of the hemicellulose-lignin matrix. We confirmed the hypothesis formulated in this paper by the cell wall surface topography, the analysis of the treated samples by Fourier transform infrared spectroscopy, and the analysis of volatiles during heating by headspace gas chromatography-mass spectrometry.