Microporous metal–organic frameworks (MOFs) have attracted tremendous attention because of their versatile structures and tunable porosity that allow almost unlimited ways to improve their properties and optimize their functionality, making them very promising for a variety of important applications, especially in the adsorption and separation of small gases and hydrocarbons. Numerous studies have demonstrated that MOFs with multifunctional groups, such as open metal sites (OMSs) and Lewis basic sites (LBSs), interact strongly with carbon dioxide and are particularly effective in its capture and separation from binary mixtures of CO₂ and N₂. In this feature article, we briefly review the current state of MOF development in this area, with an emphasis on the effect of multifunctional groups on the selectivity and capacity of MOFs for the CO₂ capture from flue gas mixtures.