The effects of vacuum heat treatment were studied relative to the chemical composition of larch wood. The samples were heat-treated in vacuum at 160 °C, 200 °C, and 240 °C for 4 h, and the chemical changes were investigated by wet chemical analysis, elemental analysis, calorific value determination, and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). The relative percentage contents of lignin and extractives increased after heat treatment. Additionally, the relative percentage contents of holocellulose, cellulose, and hemicelluloses decreased as a result of the thermo-vacuum treatment. Elemental analysis showed a slight reduction in the contents of hydrogen and oxygen. Vacuum heat treatment also increased the calorific value compared with untreated samples.