In this work, statistical analysis is used to extract pore environments from pore size distributions of crystalline representations of MOFs that feature a hierarchical pore system, namely DUT-32 , DUT-75 , UMCM-1 and NU-1000 (Fig. ). This analysis effectively partitions the entire pore volume into volume groups labelled with respect to the pore size. The pore descriptions are subsequently used to understand how the different parts of a porous framework are filled during Ar adsorption at 87 K. This is powerful analysis for understanding difficult to measure adsorption events, such as adsorbate-induced deformation, and to ascertain the distinct adsorption steps observed in interesting isotherms. To better understand the behaviour of adsorption, a method to cluster the pore environments with respect to their size and identify the centre of the pore was developed. Finally, the pore centres were used to demonstrate the distribution of gas within the pore to describe adsorbate positions during filling events from the perspective of the centre of the pore.