Wood-SiO 2 composites (WSiO 2 Cs) were prepared by means of the sol-gel process with methyltrimethoxysilane (MTMOS) as a reagent, and the physical properties, structure and thermal decomposition kinetics of the composites has been evaluated. The dimensional stability of the WSiO 2 Cs was better than that of unmodified wood, especially in terms of the weight percent gain (WPG), which achieved values up to 30%. The 29 Si-NMR spectra show two different siloxane peaks (T 2 and T 3 ), which supports the theory about the formation of MTMOS network structures. Thermal decomposition experiments were also carried out in a TG analyzer under a nitrogen atmosphere. The apparent activation energy was determined according to the iso-conversional methods of Friedman, Flynn-Wall-Ozawa, modified Coats-Redfern, and Starink. The apparent activation energy between 10 and 70% conversion is 147–172, 170–291, 189–251, and 192–248 kJ mol −1 for wood and WSiO 2 Cs with WPGs of 10, 20, and 30%, respectively. However, the reaction order between 10 and 70% conversion calculated by the Avrami theory was 0.50–0.56, 0.35–0.45, 0.33–0.44, and 0.28–0.48. These results indicate that the dimensional and thermal stability of the wood could be effectively enhanced by MTMOS treatment.