The lignan hydroxymatairesinol (HMR, extracted from Norway spruce knots) was hydrogenolysed to matairesinol (MAT) over palladium supported by carbon nanofibres (Pd/CNF) in 2-propanol at 70 °C under hydrogen flow. The influence of support acidity on the activity and the selectivity to MAT was studied. The acidity of the Pd/CNF catalyst was varied by heat-treatment at different temperatures in nitrogen flow. The catalysts were characterized by transmission electron microscopy (TEM), inductively coupled plasma emission mass-spectrometry (ICP-MS, metal content), H2-chemisorption (dispersion, metal particle size), and titration using NaOH. A more acidic support material was more active and selective to the desired product MAT. The major byproduct was 7-iso-propoxymatairesinol resulting from a reaction of the solvent with HMR over the acid sites on the support. The hydrogenolysis of HMR to MAT requires both the presence of metal and acidity.