The use of simultaneous neutron powder diffraction (NPD) and microwave characterisation can provide more information than the use of either technique individually; for example, it enables the differentiation of physisorbed and metal-coordinated species. Many possible experiments using these combined techniques can benefit from the addition of a heat source for sample heating, such as real-time measurements of solvent removal, or chemical and catalytic reactions. This paper documents the design of equipment to conduct simultaneous NPD and 2.5 GHz microwave cavity resonance techniques at elevated temperatures and confirms the use of this equipment for successful desolvation of a metal–organic framework (MOF) sample at 150 °C. The high sensitivity of microwave characterisation of lossy and polar materials is demonstrated at levels much lower than those that can be detected using crystallographic techniques.