Hemp shiv has been widely used as a plant aggregate incorporated into natural building composites such as hemp-lime due to its low thermal conductivity and high moisture buffer value. The aim of this research is to study the intrinsic physical parameters such as the porosity and cell wall structure of hemp shiv, which are responsible for the favourable thermal and hygric properties of hemp shiv. Scanning electron microscope observations of hemp shiv revealed microstructural features. A computed tomography (CT) scan improved the vizualization of pore shape and pore connectivity in three dimensions. The vessels exhibit little variation in size and there is no clear pore arrangement with a diffuse-porous distribution. The vessels are mostly solitary although some small groups of adjacent vessels exhibit shared cell walls between them. The vessels are approximately 50 to 100 μm in diameter and are surrounded by relatively thick fibre cells. These thick-walled fibres are located between the vessels with a diameter ranging from 1μm to 2μm. The pore frequency of hemp shiv (generally only measured on diffuse-porous woods) is around 20.8 vessels/mm2. The porosity of hemp shiv has been studied by a combination of mercury intrusion porosimetry (MIP) and CT scanning. Average accessible porosity of hemp shiv is 76.67 ± 2.03 % measured by MIP measurement and from 50% to 75% measured by CT, depending on the threshold and resolution