We investigated the adsorption/desorption mechanism of water and the variation of water adsorption for modern and archaeological wood using near-infrared spectroscopy. A mixture model of water was used to decompose the near-infrared difference spectra into three components (free water molecules (S 0), those with one OH group engaged in hydrogen bonding (S1), and those with two OH groups engaged in hydrogen bonding (S2)) based on a principal component analysis. The variations of each water component with relative humidity could be explained by proposing a model that describes water absorption in three stages. It was concluded that the aging phenomenon in wood is due to the decrease of adsorption sites on hemicellulose and amorphous cellulose.