Sorption of water has a profound effect on the material properties of wood. The uptake of water vapour in wood and other materials releases more heat than the condensation of vapour to liquid water. This excess energy provides insights to the interactions and energy state of the absorbed water molecules. Modification of wood by acetylation is a common way of altering the wood-water interactions; however, very few data exist on how this and other types of modification affect the energy state of absorbed water in wood. This study is the first to use sorption calorimetry on modified wood to explore the effect of acetylation on wood-water interactions. Acetylation decreased the strength of the interactions between wood and water as seen from a decrease in differential enthalpy of mixing, both overall and in the dry state. It appears that acetylation removes or hinders the most-energetic interactions or bonding configurations of water in wood, perhaps because acetylation reduces the number of water-accessible hydroxyls more than it reduces the amount of absorbed water molecules.