The UiO-66 (Zr) metal–organic framework (MOF) is of notable interest due to its facile synthesis, robustness under a wide range of chemical and physical conditions and its capability to separate industrially relevant hydrocarbons mixtures. However, the knowledge of the molecular mechanisms behind these process remains limited. Here, we present a combined experimental (2H NMR) and computational study of the molecular mobility, transport and adsorption of C5 alkanes isomers in a dehydroxylated UiO-66 (Zr) MOF. We show that the tetrahedral cages of the MOF are the preferred adsorption location for both n-pentane and isopentane. In a binary mixture of the isomers, isopentane interacts more strongly with the material leading it to occupy more of the tetrahedral cages than n-pentane, resulting in an isopentane/n-pentane adsorption selectivity of αads = 2 (at 373 K). At the same time, the microscopic diffusivity for n-pentane, Dn (En = 18 kJ mol−1), is significantly lower than for isopentane, Diso (Eiso = 28 kJ mol−1), which results in a high separation selectivity for a n-pentane/isopentane mixture of α ≈ 13 (at 300 K). This shows that the UiO-66 MOF is indeed a promising active material for use in light hydrocarbon separation processes. [ABSTRACT FROM AUTHOR]