Wood represents a highly suitable biobased scaffold for the development of mechanically robust and functional materials. Its functionalizability can be enhanced by means of delignification, resulting in an increase in porosity due to partial or complete removal of lignin and hemicellulose constituents. In this work, the impact of partial and complete delignification on the mesoporous structure is investigated via water vapor sorption isotherms and deuterium exchange. Pore size distributions of wood samples with five different delignification levels were compared to native wood. The derived pore size distributions at the water swollen state reveal an increase in porosity with decreasing lignin content. However, after complete lignin removal, drying causes a nonreversible collapse of the cell wall, which results in reduced porosity.