A deeper insight into the molecular interactions in the highly intermixed structure of the wood cell wall, from the point of view of both basic and applied science, is necessary. In particular, the role of the different matrix materials within the cell wall needs to be better understood, especially concerning how lignin contributes to the mechanical properties. In the present paper, the mechanical properties of spruce wood have been studied on a molecular scale by means of dynamic Fourier transform infrared (FTIR) spectroscopy. To this purpose, native spruce wood was subjected to chemical changes by impregnation and a mild pre-cooking with white liquor with a composition usual for kraft pulping. For comparison, lignin-rich primary cell wall material was also isolated by means of thermomechanical pulp (TMP) refining. Dynamic FTIR spectroscopy revealed that lignin took part in the stress transfer in all investigated samples. This finding is in contrast to literature data. A strong indirect coupling between lignin and cellulose was seen in the primary cell wall (P) material. In case of native wood, the lignin signal was much weaker and also indicated an indirect coupling to cellulose. In the case of pre-cooked wood samples (submitted to mild pulping), the interactions were modified so that the molecular straining of lignin was stronger and more directly related to that of cellulose. In other words, in these samples, lignin played a more active role in the stress transfer as compared to native wood. These findings were supported by a narrower lignin-softening region as measured by dynamic mechanical analysis (DMA). The interpretation is plausible in terms of the superior stiffness seen for high-yield pulps of a similar yield as the studied pre-cooked wood samples.