We will study the structural evolution of cyclodextrin-based metal-organic frameworks (CD-MOFs) upon heating and cooling using wide-angle X-ray scattering (WAXS). Thermal decomposition typically inhibits the melting of CD-MOFs, but these limitations will be overcome at the ID13 beamline, where we will combine WAXS with fast scanning calorimetry (FSC). FSC can heat CD-MOFs at rates up to 20000 K s−1, effectively outrunning decomposition. The detector at ID13 has a time resolution of just under 2 ms, enabling the real-time monitoring of the structural evolution during heating. Hence, we will unveil what melts (the ligand, the metal–ligand bond, or both), the porosity of molten CD-MOFs, and whether the melt will reassemble into the original CD-MOF structure upon cooling. Hence, we will gain unprecedented insights into the liquefaction and solidification of CD-MOFs. By applying FSC to melt MOFs for the first time, we will pave the way for studies on novel liquid MOF classes.