Thermomicroscopy (aka hot-stage microscopy) has been shown to be an excellent complimentary tool when used in conjunction with other analytical techniques, such as DSC and TGA. The optical data obtained from thermomicroscopy aid in the elucidation of complex events, often seen in many thermoanalytical profiles. Here, a system linking hot-stage microscopy and direct analysis in real-time mass spectrometry is described. This combination allows the simultaneous detection of both physical and chemical properties of a material as it is heated. Results showcasing the benefits of this combination include the thermal separation of energetic materials, the analysis of 3D printer filaments, and the profiling of trace materials including paint chips and fibres.