AbstractSeparation is an important industrial step with critical roles in the chemical, petrochemical, pharmaceutical, and nuclear industries, as well as in many other fields. Although much progress has been made, the development of better separation technologies, especially through the discovery of high‐performance separation materials, continues to attract increasing interest due to concerns over factors such as efficiency, health and environmental impacts, and the cost of existing methods. Metal–organic frameworks (MOFs), a rapidly expanding family of crystalline porous materials, have shown great promise to address various separation challenges due to their well‐defined pore size and unprecedented tunability in both composition and pore geometry. In the past decade, extensive research is performed on applications of MOF materials, including separation and capture of many gases and vapors, and liquid‐phase separation involving both liquid mixtures and solutions. MOFs also bring new opportunities in enantioselective separation and are amenable to morphological control such as fabrication of membranes for enhanced separation outcomes. Here, some of the latest progress in the applications of MOFs for several key separation issues, with emphasis on newly synthesized MOF materials and the impact of their compositional and structural features on separation properties, are reviewed and highlighted.