The approach applied to DUT-32 provides the pore-centred atomistic environment of p1, p2 and p3, as illustrated in Fig. . The pores p1 and p2 are observed to be very different in structure, which leads to different adsorption sites. The radial distribution demonstrates p2 has a defined adsorption site at ≈ 12 Å, associated with the face of the planar tritopic ligand. No obvious site is observed for p1, which leads to preferential adsorption in p2 observed in the pore isotherms (Fig. ). The first step in the isotherm is observed in all pores of this material. We can see this in the radial plots of the fourth point, where a drastic increase in number of molecules is observed for each pore. The adsorbed phases after this step extends from the surface of p1 and p2 to the centre of the pore but only extends ≈ 5 Å from the pore wall in p3 The localisation suggests the first step is associated with pore saturation of both p1 and p2 that triggers an adsorbed layer to form in p3. After this initial step only a small amount of extra adsorption is observed in p1 and p2 while the increase in pressure leads to the adsorbed layer in p3 to grow up to saturation. Clearly this pore-centred view of adsorption provides a unique view of the process of adsorption in hierarchical materials leading to better understanding of pore filling mechanisms.