An important traditional load bearing member in oriental ancient timber structure buildings, i.e. Huagong (flower arm), was selected to explore the alterations in cell wall components and hygroscopic properties of wood during long time ageing. This archaeological poplar (Populus spp.) wood with cal. BP 690: BP 790 was studied from the wood surface and inwards by means of imaging FTIR spectroscopy, X-ray diffraction and dynamic vapour sorption. The deterioration of the archaeological wood mainly displayed a depolymerization of glucomannan and lignin as well as a hydrolysis of the glucuronic acid of xylan and of the aromatic C–O groups in the condensed lignins or lignin–carbohydrate complexes. Furthermore, the degradation promoted the rearrangement of the cellulose molecules in adjacent microfibrils. The cellulose crystallites in the archaeological wood were therefore packed more tightly and had larger diameter. The structural alterations of wood cell wall components and a decrease in crystallinity contributed to an increase in the number of moisture bonding sites and led to an increase in both the equilibrium moisture content of the archaeological wood in the entire RH range as well as an increase in hysteresis.