We propose to perform an in situ PXRD experiment during thermal cycling and gas adsorption on a perfluorinated AlIII-based metal-organic framework (MOF) with MIL-53 topology, dubbed F4_MIL-53(Al), at beamline BM01. The aim of the experiment is to gain detailed insight into the phase transitions occurring when the MOF is either thermally cycled or exposed to adsorptives such as N2, Ar and CO2. This is motivated by the interest in further understanding the flexible behaviour of this MOF, which features a temperature-induced phase transition and whose adsorption isotherms display several steps, suggestive of adsorption-induced phase changes. Of special interest is the fact that both the calorimetric profile and the adsorption isotherms display much smaller hysteresis than the fully hydrogenated version of the same MOF, which is the prototypical “breathing” material.