Abstract: Unlike many mineral-based insulation materials bio-based lignocellulosic fibre and shiv offer a number of benefits including thermal and hygroscopic properties. The microstructure, porosity and chemical compositions of the plant cell walls play a major role in the moisture exchange process. In this paper, the effects of microstructure, chemical composition, porosity and pore size distribution of both fibre and shiv, from hemp and flax plants, on both moisture and heat sorption were studied for the first time. The physical and chemical characteristics of the fibre and shiv from hemp and flax were studied by using scanning electron microscopy, mercury intrusion porosimetry and Fourier transform infrared spectroscopy. Water moisture sorption and heat of sorption were studied using a dynamic vapour sorption apparatus and a simultaneous thermal analysis system, combined with a humidity generator and using a copper furnace. Results showed that both the fibre and shiv of hemp and flax adsorbed a similar amount of moisture at a given relative humidity, which was dependent on the availability of hydroxyl groups for water in the cell wall. The macroscopic surface area and porosity of the specimen on a large scale had little influence on the availability of hydroxyl groups in the cell wall. The water molecules bound with cell wall molecules through hydrogen bonds over the full range of relative humidities, with a consistent hysteresis difference between the first sorption isotherm and subsequent sequential sorption cycles found in the hemp shiv specimens. For both hemp and flax, the isothermic hysteresis of the shiv was much higher than that of the fibre, which was shown to be dependent on the lignin content. The result of heat sorption indicated that some blocked sorption sites become available to water vapour molecules due to the change in molecular structure of the cell wall during the adsorption process. This study has improved understanding of the hemp and flax sorption behaviour and is important for optimal application of bio-based insulation materials for construction.