Hemp blocks, also known as hempcrete, are eco-friendly and sustainable construction materials composed of hemp, lime, and water. In this study, the fire behaviour and structural performance of hemp-based materials were experimentally investigated. Fire exposure scenarios using raw hemp shives, hemp blocks, and non-load-bearing hemp block walls were examined. Tests conducted include cone calorimeter, bomb calorimeter, standard furnace, heat-transfer rating inducing system (H-TRIS), and small-scale elevated temperature material tests. Hemp shives exhibit ignition with sustained flaming, a relatively high heat release rate (HRR), and a relatively low critical heat flux (CHF). However, the hemp blocks exhibited no flaming ignition, only smouldering combustion, and an HRR an order of magnitude lower. Hemp blocks and hemp shives produced minimal smoke. Hemp blocks charred, and associated discoloration zones have been documented. Tests indicate that limited structural capacity is lost up until 200 °C, whereas at 300 °C, the residual material strength is almost negligible. The hemp block walls maintained their structural stability and integrity for 2 h of standard fire testing. The ambient-temperature compressive strength of the hemp blocks was determined to be 1.0 MPa. This work is the first comprehensive study on the fire behaviour of hemp blocks and highlights their good performance, whereby they are likely to have a limited impact on fire risk in buildings. Plastered walls will have a fire performance exceeding those reported here.