Conventional separation technologies for valuable commodities require substantial energy, accounting for 10%–15% of global consumption. Mixed-matrix membranes (MMMs) offer a promising solution by combining processable polymers with selective inorganic fillers. Here, the potential of using ordered microporous structured materials is demonstrated as MMM fillers. The use of ordered macroporous ZIF-67 in combination with the well-known 6FDA-DAM polymer leads to superior performance in the important separation of propylene from propane. The enhanced performance can be rationalized with the help of advanced microscopy, which demonstrates that the polymer is able to penetrate the macroporous network around which the MOF (Metal-Organic Framework) is synthesized, resulting in a much better interphase between the two components and the homogeneous distribution of the filler, even at high loadings.